Review

Cite This: Chem. Rev. 2018, 118, 6297−6336 pubs.acs.org/CR

van der Waals Metallic Transition Metal Dichalcogenides

Gang Hee Han,†,‡,∥ Dinh Loc Duong,†,‡,∥ Dong Hoon Keum,†,‡ Seok Joon Yun,†,‡
and Young Hee Lee*,†,‡,§
†
Center for Integrated Nanostructure Physics (CINAP), Institute for Basic Science (IBS), Suwon 16419, Republic of Korea
‡
Department of Energy Science, Sungkyunkwan University, Suwon 16419, Republic of Korea
§
Department of Physics, Sungkyunkwan University, Suwon 16419, Republic of Korea

ABSTRACT: Transition metal dichalcogenides are layered materials which are

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composed of transition metals and chalcogens of the group VIA in a 1:2 ratio. These
layered materials have been extensively investigated over synthesis and optical and
electrical properties for several decades. It can be insulators, semiconductors, or metals
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revealing all types of condensed matter properties from a magnetic lattice distorted to
superconducting characteristics. Some of these also feature the topological manner.
Instead of covering the semiconducting properties of transition metal dichalcogenides,
which have been extensively revisited and reviewed elsewhere, here we present the
structures of metallic transition metal dichalcogenides and their synthetic approaches for
not only high-quality wafer-scale samples using conventional methods (e.g., chemical
vapor transport, chemical vapor deposition) but also local small areas by a modification of
the materials using Li intercalation, electron beam irradiation, light illumination, pressures, and strains. Some representative
band structures of metallic transition metal dichalcogenides and their strong layer-dependence are reviewed and updated, both
in theoretical calculations and experiments. In addition, we discuss the physical properties of metallic transition metal
dichalcogenides such as periodic lattice distortion, magnetoresistance, superconductivity, topological insulator, and Weyl
semimetal. Approaches to overcome current challenges related to these materials are also proposed.

CONTENTS 4.1.4. 1T-, 2H-, and 4H-TaS2 6310

4.2. Layer Dependence of the Band Structure in
1. Introduction 6298 Metallic Layered Transition Metal Dichalco-
2. Crystal Structures of Layered Transition Metal genides 6310
Dichalcogenides 6299 5. Periodic Lattice Distortion or Charge Density
2.1. Structural Classifications 6299 Wave in Matallic Layered Transition Metal
2.1.1. H and T Phases 6299 Dichalcogenides 6311
2.1.2. Extended Structures 6299 5.1. Periodic Lattice Distortion Phenomenon 6311
2.2. Other Layered Transition Metal Dichalcoge- 5.2. Mechanism for Periodic Lattice Distortion
nides and Related Compounds 6301 Transition 6311
2.3. Table of Metallic Layered Transition Metal 5.3. Experimental Characterization of Periodic
Dichalcogenides Structures 6301 Lattice Distortion 6316
3. Synthesis 6301 5.4. Tuning Periodic Lattice Distortion Transition
3.1. Bulk Single Crystal Growth 6301 and Superconductivity Phase Formation 6317
3.1.1. Flux Method 6301 6. Other Properties 6319
3.1.2. Chemical Vapor Transport 6303 6.1. Magnetism in 2D Metallic Layered Transi-
3.2. Chemical Vapor Deposition 6303 tion Metal Dichalcogenides 6319
3.3. Other Synthetic Methods 6305 6.1.1. Magnetism in 2D Materials and Mag-
3.3.1. Molecular Beam Epitaxy 6305 netic Metallic Layered Transition Metal
3.3.2. Li-Intercalation 6305 Dichalcogenides 6319
3.3.3. Phase Transition by Laser and e-Beam 6.1.2. Ferromagnetism in Atomically Thin 2D
Irradiation 6306 Metallic Layered Transition Metal Di-
4. Electronic Structures 6306 chalcogenides (VS2 and VSe2) 6320
4.1. Electronic Structures of Representative
Metallic Layered Transition Metal Dichalco-
genides 6306
4.1.1. 1T-TiS2 and 1T-TiSe2 6310 Special Issue: 2D Materials Chemistry
4.1.2. 1T-VSe2 6310
Received: October 15, 2017
4.1.3. 1T- and 2H-NbSe2 6310
Published: June 29, 2018

© 2018 American Chemical Society 6297 DOI: 10.1021/acs.chemrev.7b00618

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6.1.3. Strain Effect on Magnetism of Metallic area. Weyl semimetals and phase engineering associated with
Layered Transition Metal Dichalcoge- contact resistance are examples of newly adopted research area
nides 6322 in m-LTMdCs.8−10 In the synthetic point of view, some
6.1.4. Doping Effect on Magnetism of Metallic advances have been made through chemical vapor deposition
Layered Transition Metal Dichalcoge- method (CVD). Monolayer LTMdCs are easily accessible by
nides by Vacancy, Hydrogenation, and CVD, which is rather difficult to obtain by other platforms
Substitution by Dopants 6323 such as CVT or flux methods. Recent studies on m-LTMdCs
6.2. Weyl Semimetal in 1Td WTe2 and MoTe2 6324 have not been conducted much compared to the semi-
7. Summary and Perspectives 6326 conducting components. Many physical and chemical
Author Information 6327 phenomena are still being studied in m-LTMdCs.
Corresponding Author 6327 This review consists of seven sections including the
ORCID 6327 Introduction. In the next section, we introduce the basic H
Author Contributions 6327 and T structures of LTMdCs and their extended structures by
Notes 6327 considering stacking sequences. We also briefly introduce the
Biographies 6327 metal chalcogenides which has different stoichiometric ratios
Acknowledgments 6328 such as 1:1 or 2:3 or ternary (quaternary). However, the
Abbreviations Used 6328 properties of those materials are out of scope and excluded in
References 6328 this thematic review. We provide them in the form of a table at
the end of the section. In section 3, we introduce various
synthesis methods. A brief description of the flux and the CVT
1. INTRODUCTION methods for the bulk materials are discussed. In particular,
Two-dimensional (2D) van der Waals (vdW) layered section 3.2 summarizes the conventional CVD approaches,
materials, which have a strong covalent bonding within the which have been developed typically for the synthesis of s-
layer and weak vdW interaction between the layers, reveal LTMdC to date. The process can be extended for the growth
themselves as having unique layer-dependent features distinct of m-LTMdCs. We also briefly introduce the molecular-beam
from bulk materials. For example, graphene is one of the epitaxy method (MBE) and the phase transition of s-LTMdCs
intensively studied species1 due to their remarkable electrical to m-LTMdCs through intercalation, laser, or e-beam
and optical properties since 2004. In addition, many of layered irradiation in the last section of section 3.
materials have been discovered for a decade. Boron nitride has It is important to understand the electronic band structure
been considered as a template to improve the carrier mobility of materials. Combined with the theoretical calculation and the
of graphene compared to conventional insulator substrates angle-resolved photoemission spectroscopy (ARPES), the
such as SiO2.2 Other 2D materials, such as black phosphorus,3 band structure of materials are now more clearly visible.11,12
borophene,4 silicene,5 and stanene,6 also join the 2D family. In Section 4 discusses the band structure of m-LTMdCs. We
addition, there are numerous compounds consisting of provide the electronic structures of transition metals and
transition metals and chalcogens to form a large category of chalcogens and compare the band structures of representative
layered transition metal dichalcogenides (LTMdCs). Revisiting m-LTMdCs such as TiS2, TiSe2, and VSe2 with theoretical
of the first LTMdCs has been made from the semiconducting calculations and experimental works determined from ARPES.
species such as MoS2, which has long been known as lubricant We further introduce the electronic band structures of the bulk
similar to graphene. Intriguing physical properties of a number NbSe2 and TaS2, which have both H and T phases. Layer
of semiconducting LTMdCs (s-LTMdCs) species have already dependence will be discussed in the last part of section 4. The
been discussed elsewhere.7 density functional theory (DFT) is the most versatile and
Unlike s-LTMdCs, metallic LTMdCs (m-LTMdCs) (Figure common approach for band structure calculations.13,14 The
1) have a finite density of states at the Fermi level and their main idea of the DFT is to replace the wave function basic set
research fields rather differ from semiconducting materials. by the electron charge density, which is called the mean field
Therefore, it is worth revisiting some research topics that are approximation.15 By this methodology, the huge number of
well-known in 3D materials such as charge density wave electrons can be treated as the electron density, which is a
(CDW) or periodic lattice distortion (PLD), superconductiv- three-dimensional space function with three degrees of
ity, magnetism in metallic 2D vdW materials. Recent freedom. However, this approach gives rise to difficulties in
progresses in m-LTMdCs has further expanded the research estimating the exchange (e.g., the interaction originated from
the indistinguishable nature of electrons) and correlation (e.g.,
the energy error when treating electron clouds as an
independent object) of electrons. It is the motivation for the
development of varieties of different exchange-correlation
functions from the local density approximation, generalized
gradient approximation to hybrid functionals.16−18 In this
section, the band structure using different functionals for one
material will be also presented.
The appearance of the PLD phases accompanying the
Figure 1. Types of metals involved in layered dichalcogenides. Blue superconductivity transition occurs in many m-LTMdCs,
color indicates transition metals for currently developed metallic- which makes this class of layered materials attractive to
layered dichalcogenides (m-LTMdCs), and yellow, green, and red condensed matter physicists. This issue is the main focus of
small rectangles are S, Se, and Te compounds. White rectangles for section 5. The phenomenon of the PLD transitions and their
chalcogen are unreported or nonexist phase in m-LTMdCs. mechanism are described by the intuitive picture of one-
6298 DOI: 10.1021/acs.chemrev.7b00618
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Figure 2. Two primary phases for 1:2 (metal:chalcogen) ratio LTMdCs: (a) H phase, (b) T phase.

dimensional Peierls distortion. It is worth noting that the PLD Because H and T phases do not guarantee the material
transition introduces a lower symmetry structure, which breaks property as semiconducting and metallic, respectively, we
the degeneracy of the electronic band of the normal phase. cover both main structures of LTMdCs. However, in this
This is similar to the Jahn−Teller effect in chemistry, where thematic review, we limit our discussion to the physical
molecules have a tendency to distort their structure to lower property of metallic one, which have not been intensively
symmetry. As a consequence, one energy level will split to form studied as much as semiconducting LTMdCs but potentially
many states, where electrons can occupy a lower energy have many intriguing physical and chemical properties.7,20−22
configuration compared to the one of higher symmetry 2.1.1. H and T Phases. LTMdCs, either semiconducting
structures. In contrast, the Peierls model only considers one or metallic phase, consist of two tetrahedrons (Figure 2). Each
band model without any degeneracy. We will discuss how to blue tetrahedron describes the framework of the H and T
extend the Peierls model to the PLD transition in real phases with ball-and-stick models; blue and yellow atoms
materials. We will clarify that it is not necessary to fully open a indicate transition metals and chalcogens, respectively. The
band gap to maintain the low energy state of the PLD phase. lower and upper tetrahedrons are arranged symmetrically from
The phonon softening phenomenon and its relation to the metal surface (center) to form a trigonal prismatic
superconductivity, which always occurs with the PLD structure (H-phase) (Figure 2a). Another primary unit, an
transition, will be reviewed. The correlation with the Kohn octahedral or T phase, shown in Figure 2b, is constructed by
anomaly, which also reveals the phonon softening due to the rotating the upper (or lower) tetrahedron by 180°. The top
change of the electron screening, is also examined. We will also view of H phase (Figure 2a, inset) shows a hexagonal structure
discuss characterization methods for determining the PLD similar to hexagonal boron nitride (h-BN) from the top view.
phase transformation. However, in reality, two identical chalcogen layers are divided
Recently, the emergence of topological matters and 2D up and down with respect to the metal layer. In the T phase,
ferromagnetism brings attentions to m-LTMdCs, which is chalcogen atoms in the top layer are projected among
discussed in section 6. In detail, we introduce the chalcogen atoms in the bottom layer. (Figure 2b, inset)
ferromagnetism in VS2 and VSe2 and discuss the effect of 2.1.2. Extended Structures. Stacking sequence affects
strain, doping, and defects on the magnetic properties. In prominent physical properties of the materials such as
particular, we will briefly discuss the concept and band electronic band structures,23 phonon vibrations,24 and optical
structure of Weyl semimetals, which is emerging in the 1T properties. 25,26 The numbers appearing in the phase
phase MoTe2 and Td phase WTe2 and their alloy formation. nomenclature such as “2”H, “1”T, “3”R, and “4”H indicates
The last section summarizes issues and perspectives of the stacking sequence of LTMdCs. For example, 2H-MoS2
synthesis, phase transition, devices, and physical properties.
indicates the grouping of two layers with AB-stacking, while
The possibility of phase transition through the alloy and the
3R-NbS2 describes the repeating of three layers as one group,
remaining issues on superconductivity and Weyl semimetals
ABC stacking. Top and side views of the extended structures
will be also discussed.
are shown in Figure 3. The 2H structure is involved in the
2. CRYSTAL STRUCTURES OF LAYERED TRANSITION hexagonal group (group name: P63/mmc); the top view shows
METAL DICHALCOGENIDES a hexagonal lattice by alternating two chalcogen atoms and one
transition metal atom. While the majority of 2H structures in
2.1. Structural Classifications LTMdCs exhibit semiconducting properties, very few 2H
Chalcogen elements are highly reactive to metals, creating a phases are known to be m-LTMdCs including 2H-NbS2, 2H-
number of metal chalcogenide combinations with various NbSe2, 2H-TaS2, and 2H-TaSe2.27−30 The 1T phase is the
stoichiometric ratios. Among these compounds, LTMdCs have primary structure which belongs to the hexagonal group
layered structures with a 1:2 ratio between the metals and (P3̅m1) in m-LTMdCs. The structure formed is an octahedron
chalcogens.19 The unit structure of the LTMdCs includes a rather than a trigonal prismatic due to the rotation of one
transition metal layer sandwiched between two layers of tetrahedron. We discuss the material properties in other
chalcogen atoms. Metal-chalcogen atoms form strong covalent sections.
bonds within the layer. Each layer is stacked vertically by a Dimerization of transition metal atoms induces the
weak vdW interactions, and the layered bulk can typically be distortion of the 1T structure to form the 1T′ phase (P21/
exfoliated into individual layers. In the following sections, we m). In particular, dimerization of the metal atoms induces
introduce the basic structure of H and T phases of LTMdCs. displacement of chalcogen atoms in an out-of-plane direction
6299 DOI: 10.1021/acs.chemrev.7b00618
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Figure 3. Various phases and stacking sequences in LTMdCs.

and a symmetry transformation from 3- to 2-fold. 1T′-MoTe2 between 1T and Td is the c-axis angle (α ≠ 90, β = 90), as
is a representative material in m-LTMdCs.8 The Td structure, indicated in Figure 3. The 3R-phase (R3m) includes three
found in WTe2,31 is similar to the 1T′ structure. The difference layers in the unit cell. For example, NbS2, NbSe2, TaS2, and
6300 DOI: 10.1021/acs.chemrev.7b00618
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Figure 4. Other types of LTMdCs and metal-chalcogen compounds. (a) Ternary or quarternary structures for metal or chalcogen exchange without
structural transformations. (b) Layered ternary structure with other compounds such as MnPS3. (c) 1:1 ratio layered metal chalcogenide. (d)
Quintuple layered compounds such as Bi2Se3 and Bi2Te3.

TaSe2, which appear in both H and T phases, also have 3R common metal chalcogenides, this review covers only a 1:2
phases.27−30,32 Two different stacking orders exist in the 4H ratio layered TMDLTMdCs.
phase. The 4H structure in Figure 3 is the 4Hb type, which can 2.3. Table of Metallic Layered Transition Metal
be described as an alternating phase of T−H−T−H layers, Dichalcogenides Structures
while the unit cell of the 4Ha structure is composed of only H A list of m-LTMdCs is provided in Table 1. The first and
phase layers.33−41 second columns show types of transition metals and
2.2. Other Layered Transition Metal Dichalcogenides and chalcogens, respectively. The metal column includes transition
Related Compounds metal species such as Ti, V, Ni, Zr, Nb, Pd, Hf, Ta, Ir, Pt, Mo,
and W, which combined with chalcogens such as S, Se, and Te.
In addition to the typical stoichiometry of 1:2 ratio m-
(See the refs. 8 ,11, 12, 31, 41, 42, 44, 45, 52−138 in the table.)
LTMdCs, there are other types of transition metal
The semiconducting components (s-LTMdCs) such as 2H
chalcogenides and compounds. Figure 4a shows a typical T phase WSe2 and MoSe2 are not included in this table. The
phase m-LTMdC structure, for example, that of TiS2 and VS2 third column describes the corresponding phases for each
or their selenide compounds. Each pure material exhibits metal-chalcogen combination. H, T, and R are the acronyms of
metallic behavior.42,43 Figure 4a depicts alloy formation of TiS2 hexagonal, tetragonal, and rhombohedral structures, respec-
and VS2 to form TixV1−xS2 and TixV1−xSe2, or TiSxSe1−x or tively. In the table, we categorize the synthetic approach as
VSxSe1−x which maintain a 1:2 metal:chalcogen ratio while the bulk crystal growth, thin film deposition, and monolayer
topology does not change by alloying.44,45 This atomic growth of LTMdCs. To avoid confusion, we define the thin
exchanges, whether it is called alloying or doping, could film as “the film has several to hundreds layers that exhibits
induce its modulation on electrical and phononic properties. bulk properties”.
Figure 4b shows the structure of the transition metal
phosphorus trichalcogenides (C12/m1, monoclinic) or phos- 3. SYNTHESIS
phochalcogenides, typically abbreviated as MPX3 (M, metal; P, In this section, we discuss several synthetic approaches for m-
phosphorus; X, chalcogens), which is a new class of layered LTMdCs. We have categorized the sections into (i) bulk
materials for spintronics.46,47 growth, (ii) film growth including both few layers and
Figure 4c shows a material with 1:1 stoichiometry between monolayer flakes, and (iii) other synthetic methods. The
metal and chalcogen atoms. For example, FeSe has a tetragonal bulk growth section includes flux and CVT methods. Followed
structure (P4/nmm).48 From the Fe plane, chalcogen atoms section introduces the CVD process which is a representative
are alternately positioned in a z-direction. Fe sites can be approach for the materials growth as film formation. With
replaced or doped by Cu atoms. These materials have MBE and several other approaches, we also briefly introduce
intriguing physical properties such as high-temperature super- the phase changes by post-treatments such as Li intercalation,
conducting above 100 K on the strontium titanate (SrTiO3) laser, and e-beam irradiation in the last section of this chapter.
substrate.49 Metal chalcogenides which have 2(metal):3- 3.1. Bulk Single Crystal Growth
(chalcogen) forms a quintuple layer. Bi2Se3, Bi2Te3, and 3.1.1. Flux Method. The flux method is one of the
Sb2Te3 are representative materials for this quintuple layer traditional methods which provides a high-quality single crystal
arrangement and well-known as good thermoelectric materials. in bulk form. To form a crystal, raw materials are liquefied in a
These materials also reveal characteristics of topological solvent flux at high temperature (Figure 5a). The process
insulators.50,51 Since there are numerous combinations of requires the type of crucible that does not react with the
6301 DOI: 10.1021/acs.chemrev.7b00618
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 Table 1. Table for m-LTMdCs and Their Synthesis Methodsa
synthesis approaches
single and poly crystal film monolayer
metals chalcogens phase annealing flux CVT others CVD MBE others CVD MBE others
Ti S T 44, 45, 52 53, 54
Chemical Reviews

Se T 45, 52, 55 56 57 58,59

Te T 45,52

V S T 60
Se T 61,62 63 64 65
Te T 66

Zr S T 52, 67 42 68 69, 70
Se T 41, 42, 67 71

Nb S H,T, R 72 73, 74, 75

Se H,T, R 76 77, 78 79 80,81
Te T 82 83, 84

Pd Te T 85, 86 87 (B.T)

Hf Te T 88, 89 90

6302
Ta S H, T, R 91, 92, 93 94, 95 96
Se H, T, R 97, 98 99
Te T′ 100

Ir Te T 101

Pt S T 86 102 103
Se T 86 102 104, 105 106 106 107
Te T 86 102

Mo S T (mix) 108, 109, 110, 111, 112, 113, 114

Te Td, T′ 8, 12, 115 11, 116, 117, 118 119, 120, 121
122, 123, 124 125, 126, 127 128, 129, 130

W Te Td, T′ 131, 132 31, 133 134 135 127, 136 137, 138
a
The first and second columns are the types of transition metals and chalcogens, respectively. Only metallic components are shown, semiconducting (insulating) components are not included. Each
number in the table is a reference number. For 1T-MoS2, refs 108−111 and 113 are monolayer and 112 is few layers samples. Reference 114 includes both mono and few layers experimental data.
Review

Chem. Rev. 2018, 118, 6297−6336

DOI: 10.1021/acs.chemrev.7b00618
Chemical Reviews Review

Figure 5. Illustrations of the (a) flux method and (b) chemical vapor transport (CVT) method. (c) 1T′-MoTe2 crystal by flux method. Reproduced
with permission from ref 115. Copyright 2016 American Physical Society. (d) WTe2 crystal from flux method. Reprinted with permission from ref
31. Copyright 2014 Macmillan Publishers Ltd.

reactants and tolerates high-temperature treatments. In transport agents are typically pure halogen elements or their
addition, a flux material should have a low melting point so compounds, which react easily with the raw materials. Then,
that it can surround the source materials as liquid form and a the reactants are converted into forms which can be easily
high boiling point to avoid vaporization during reaction. vaporized to facilitate transportation. Therefore, the transport
Moreover, it should be easy to remove the flux after synthesis. agent should be carefully selected. By reacting metals (M:Ti, V,
NaCl, Sn, and Te fulfill all mentioned requirements and are Ni, Zr, Nb, Pd, Sn, Hf, Ta, Ir, Pt, Mo, W) and chalcogens (X:S,
typically adopted as the flux materials, as shown in Table 2. Se, Te) with a selected transport agent, MX2 structures can be
created in various combinations. The total transport process in
Table 2. Growth conditions of MoTe2 and WTe2 in the Flux the ampule is governed by the chemical equation shown
Method below:
flux conditions MA(g) + 2X(g) → MX 2(s) + A 2(g)
metals chalcogens ref temperature (°C) flux where A is the transport agent. Typically, halogen elements
Mo Te 8 1000 NaCl such as I2 or Br2 are used as transport agents. Cl2 exists in the
12, 115 1000 Te gaseous form in room temperature, which is rather dangerous.
Instead, it can be supplied as metal halides compounds such as
W Te 131 825 Te TaClx, MoClx, and PtClx. It is noticed that most of these
132 1000 Te materials are unstable or hygroscopic in an air environment,
and hence an oxygen- or moisture-free environment is
necessary. The CVT conditions for m-LTMdCs are listed in
The process enables the formation of single crystal at low Table 3. The variables are growth temperatures (hot and cold
temperatures. The solute is slowly solidified during cooling zones), types of transport agents, transition metals, and
process and eventually crystallized and precipitated out into a chalcogens. Even if there is a transport agent, a temperature
single crystal. During the process, the reduction of the solute gradient is required for the deposition of materials as described
due to the solidification in the flux lowers the reaction in table.
temperature. Several m-LTMdCs have been synthesized with
this approach.8,12,131,115,132 For examples, 1T′-MoTe2 and 3.2. Chemical Vapor Deposition
WTe2, which are representative m-LTMdCs, have been Chemical vapor deposition (CVD) provides LTMdCs as films.
synthesized with Te and NaCl fluxes, respectively. In This conventional method has been widely adopted to
particular, MoTe2 has low (H- or α-, semiconducting) and implement high-quality LTMdCs on a large-scale film. The
high temperature (T- or β-, metallic) phases. Typically, a first CVD method we introduce here is the chalcogenization of
quenching (rapid cooling) process at a high temperature is thin (few to tens of nanometers) metal films on insulating
required in order to obtain 1T′ phase MoTe2.8 substrates, which is referred to as the metal film CVD
3.1.2. Chemical Vapor Transport. Chemical vapor (MFCVD). In this method, a metal, which is one of the raw
transport (CVT) is another representative approach for a materials required to form LTMdCs, is preliminarily deposited
single crystal growth in bulk form. A number of materials, from as a film and then chalcogenized at a high temperature reactor.
simple halide to complex multinary oxide-based compounds, This approach has been conducted steadily since the early
have been synthesized by the CVT method including m- stage of CVD synthesis for LTMdCs. Figure 6a shows the
LTMdCs. A typical experimental scheme is shown in Figure schematic of typical MFCVD method. In detail, a few
5b. In this process, raw materials are transported to the nanometers of Mo was deposited using a magnetron sputter
substrate (if embedded) or inner wall of the ampule in the or e-beam evaporator.119,120 Te vapor injection at high
growth (cold) zone with the assistance of transport agents to temperature convert the pure Mo to MoTe2 film. The process
form crystals. H (hot) and C (cold) indicate high and low was firstly developed for the growth of MoS2 and adopted for
temperature zones of the reaction tube in Table 3. The the growth of other LTMdCs. The grown films are typically
6303 DOI: 10.1021/acs.chemrev.7b00618
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Table 3. Growth Conditions for the CVT Method with LTMdCs such as 1T′-MoTe2, WTe2, and PtSe2 have been
Various Transition Metals and Transport Agentsa reported by the MFCVD method.105,119,135 On the one hand,
it is advantageous to use oxide film instead of pure metal film.
CVT conditions
Phase controlled growth is an example. Oxide deposition
metals chalcogens ref H (°C) C (°C) TA (MoO3) enables 2H MoTe2 growth whereas 1T′ MoTe2
Ti S 52, 44, 45 900 800 I2 growth was preferred in pure metal chalcogenization.120
800 720 I2 Because reactions favor a direction that minimizes volume
900 700 I2, S change, 2H phase (47%) is preferable compared to 1T phase
Se 52, 45, 55 900 800 I2 (380%) MoTe2 during MoO3 tellurization. On the other hand,
780 740 I2 with oxides, it is able to grow monolayer LTMdCs when a
880 790 Se2 small amount of oxide is constantly codeposited with the
Te 52, 45 900 800 I2 chalcogen on the target substrate. This is beneficial to attain
750 690 I2 large grains of LTMdCs. Both techniques are named as metal-
oxide CVD (MOxCVD) (Figure 6b) in this review since we
V Se 61− 65 850 800 I2 classify the types of CVD according to the chemical form of
870 780 Se2 precursors. Growth of NbSe2 and 1T′-MoTe2 through this
Te 66 I2 platform has been reported.120,139 This growth platform
requires further validation for materials which has extreme
Zr S 52, 67 900 850 I2 evaporation temperatures such as HfOx (approximately 2500
1010 930 I2 °C). Oxides must be reducible during the growth process.
900 850 I2 Unlike the conventional CVD approaches, the metal-halide
Se 42,67 900 800 I2 CVD (MHCVD) method uses metal halide precursors, which
850 800 I2 is also similar to CVT method. In particular, the use of metal-
halides, in principle, coincides with the use of pure halogens
Nb S 72 850 800 I2 such as Cl, Br, and I and metal elements in the CVT process.
950 850 I2 Then, the metal precursors transforms into the metal halides
Se 76−78 730 700 I2 forms which can be easily vaporized. It eventually provides
780 I2 high-quality crystals. However, precursors are typically
Te 82−87 900 850 I2 sensitive to oxygen and (especially) moisture in the air. Figure
1000 I2 6c shows the typical setup for MHCVD. S chips and HfCl4
powder are located in the inner tubes in the upstream zone.
Sn S 52, 40 950 600 I2 Because the HfCl4 precursor has a lower vaporization
950 850 I2 temperature (310 °C in the experiment), HfS2 (s-LTMdCs)
was successfully grown with the method.140 Several m-
Hf Te 88, 89 800 500 I2 LTMdCs have been carried out by this approach. TiCl4,
800 I2 VCl4, ZrCl4, and NbCl5 used as metal-halide sources for the
growth of TiS2 and TiSe2, VS2 and VSe2, ZrS2 and NbS2, and
Ta S 91−93 850 800 I2 NbSe2, respectively. We also assign H2PtCl6 for the synthesis
950 300 I2 of PtSe2 in this category (see Tables 4 and 5)
700 650 Cl2 The metal−organic CVD (MOCVD) method was used in
Se 97, 98 725 700 I2 the 1990s for the synthesis of m-LTMdCs, notably for the
1050 1000 I2 production of TiS2 through the introduction of Ti(S-t-Bu)4.53
700 650 Cl2 It is adventageous that the precursor has low decomposition
Te 100−102 850 750 Cl2
temperatures compared to pure metals or oxides because the
bonding between metal and organic component are weak.
Pt S 103 800 740 Cl2
These materials are highly toxic and therefore should be
handled with care. MOCVD has recently been adopted to
Mo Te 116−118, 11 1000 900 TeBr4
synthesize s-LTMdCs (Figure 6d). Metal−organic precursors
1000 900 TeCl4
such as Mo(CO)6, W(CO)6, and (C2H5)2S were introduced
1000 900 I2
for growing wafer-scale MoS2 and WS2.141 The approach has
not yet been extended for the growth m-LTMdCs except 1T′-
W Te 31, 133 750 650 Br2
MoTe2.142 Metal precursor can also be prepared as a solution
950 775 Br2
a
type (water or organic liquid medium). For example,
H (hot) and C (cold) are the temperatures of the tube. TA is an (NH 4 ) 6 Mo7 O 24 143 and (NH4 ) 2 MoS 4 144 are soluble in
abbreviation of transport agent. deionized (DI) water and organic solvent, respectively,
followed by dipping or spinning on the substrate (liquid
thicker than the initially deposited metal film due to the source CVD, LSCVD). Such materials eventually decompose
volume expansion by metal-chalcogen reaction. In some cases, into metal oxides form therefore annealing the substrate with
the approach induces cracking and surface roughening of the (or without) extra chalcogens produces monolayer LTMdC or
film. Control of the reaction speed can resolve this issue.119 continuous film (few layers). A mixture of the metal oxide and
Scalability and accessibility are the advantages of MFCVD its chloride can facilitate the metal−chalcogen reaction to
method. However, the grain size is relatively small compared to create huge flakes−hybrid CVD (HCVD). In the work,127
other conventional approaches to be introduced. Few m- metal oxide−metal chloride−Te precursor in a 1:1:1 ratio was
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Figure 6. Various chemical vapor deposition (CVD) methods for film and monolayer growth are shown. (a) Metal film (predeposited) CVD;
MFCVD. Reproduced with permission from ref 119. Copyright 2015 American Chemical Society. (a) Metal oxide (predeposited) CVD;
MOxCVD. Reproduced with permission from ref 120. Copyright 2015 American Chemical Society. (c) Metal halide CVD; MHCVD. Reproduced
with permission from ref 140. Copyright 2016 IOP Publishing. (d) Metal organic CVD; MOCVD. Reproduced with permission from ref 141,
Copyright 2015 Macmillan Publishers Ltd.. (e) Liquid source CVD; LSCVD. Reproduced with permission from ref 125. Copyright 2016 IOP
Publishing. (f) Hybrid CVD (oxide and chlorine precursor); HCVD. Reproduced with permission from ref 127. Copyright 2017 Wiley.

introduced at the downstream zone with extra Te vapor from formation of WTe2 on bilayer graphene graphitized from
the upstream zone to synthesize 1T′-MoTe2 and WTe2, which 6H-SiC(0001). It shows the semiconducting behavior at low
are both m-LTMdCs. Table 4 and 5 show various growth temperatures.153
conditions for CVD approaches. 3.3.2. Li-Intercalation. Intercalation is the process that
3.3. Other Synthetic Methods inserting the ions into a layered material. In LTMdCs, typically
alkali metal ions have been used as guest materials, which
3.3.1. Molecular Beam Epitaxy. Since the development induces structural changes due to the charge transfer from the
of molecular beam epitaxy (MBE) in the 1960s, this technique guest (ion) to the host material (LTMdCs). For an example,
has been widely adopted for ultrahigh quality film growth in phase transition from semiconducting 2H to metallic 1T
the laboratories and industry. With MBE techniques, described phases takes place during the intercalation process in MoS2.
in Figure 7a, growth typically carried out in ultrahigh vacuum Many applications using LTMdCs have been reported such as
(UHV) as high as 10−12 Torr with controllable growth rate supercapacitors, batteries, and hydrogen evolution reaction
which is precise, in principle. The purity (or quality) of film is (HER) catalysts.154,155 The phase transition by chemical
extremely high compared to the achievements from the other treatment also applied to the bulk LTMdCs materials. One
synthetic approaches. The growth of vdW layered materials, of the advantage is that Li intercalating compounds (or alkali
including TMDs, by MBE was initially accomplished in the metals) can chemically exfoliate bulk materials into several
1990s;146−150 several m-LTMdCs were successfully synthe- layers, even down to monolayers. The phase change occurs by
sized by MBE, as shown in the Table 5. modulating the electron injection from a semiconducting to a
The materials grown with MBE are therefore suitable for metallic one. For example, intercalation of Li-ion in MX2 (M,
investigating intrinsic physical properties, which require high metal; X, chalcogen) can be described by the following
purity and crystallinity. For example, MBE grown TiSe2 sample reaction:
clearly shows CDW phenomenon,57,59 which is discussed
separately in other section of the manuscript. TaS2 layer was MX 2 + n BuLi → [MX 2− + Bu•+ Li+]
also successfully synthesized on Au (111) substrate.96 Layer
controlled growth of PtSe2 by MBE method has been → LiMX 2 + octane
reported,106 and the material exhibits a high bulk conductivity
and intriguing Dirac semimetallic properties.151,152 Monolayer The intercalating material in chemical reaction is n-butyl
NbSe2 grown on graphene and h-BN also shows CDW lithium, a partially converted metallic (1T) phase of MoS2
phenomena and superconductivity.106 In the case of MoTe2, a obtained from the semiconducting (2H)
wide variety of substrates have been used as growth templates phase.108−112,114,156−158 Recent advances in phase transition
such as graphene,128 MoS2,106 and highly ordered pyrolytic (or engineering) offer degrees of freedom to obtain novel
graphite (HOPG).107 Bulk WTe2 is known to exhibit giant heterostructure for low contact resistance devices. For
magnetoresistance. MBE process enables a monolayer example, monolayer metal−semiconductor−metal device
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Table 4. Growth Conditions for the CVD Process (Film)a

experimental conditions for film
metals chalcogens ref type source temperature (°C) shape
Ti S 53, 54 MOCVD Ti(S-t-Bu)4 150, 270 rough film
MHCVD TiCl4 200−500 rough film
Se 56, 57 MHCVD TiCl4 250−600 plate-like film
MBE Ti metal 200−300 ultrathin film

V S 60 MHCVD VCl4 550 SC nanosheet

VOCl3
Se 64 various types V(NMe2)4 250−600 plate-like film
VCl4

Zr S 68 MHCVD ZrCl4 600−800 thin film

Se 71 ED ZrSO4 100−250 after deposition

Nb S 73−75 MHCVD NbCl5 1050 SC thin flake

MHCVD NbCl5 1000 SC thin flake
MHCVD NbCl5 800 SC nanosheet
Se 79 MHCVD NbCl5 250−650 plate-like film

Hf Te 90 MBE Hf metal 530, 650 thin film

Ta S 94, 95 MHCVD TaCl5 820 SC thin flake

CVT Ta metal 950, 300 film
Se 99 MBE Ta metal 450, 650 film

Pt Se 104, 105 MHCVD H2PtCl6 900 SC nanosheet

MFCVD Pt film 400 thin film

Mo Te 119−124 MFCVD Mo film 650 thin film

MOxCVD MoO3 film 700 thin film
MOxCVD MoO3 680 film
MFCVD Mo film 700 thin film
MOxCVD MoO3 700, 650 film
MOxCVD MoO3 film 650−800 film

W Te 134, 135 MFCVD W film 800 film

MBE W metal 275 thin film
a
Abbreviations of “type” column are listed in Figure 6and the Abbreviations section.

structure of MoS2 was fabricated by n-butyl lithium treatment under e-beam irradiation during in situ transmission electron
as shown in Figure 7b.114 Unusual electrical transport such as microscope (TEM) observation.113 The 2H phase converts
variable range hopping can also be induced by chemical into a new intermediate phase as described α in the literature.
treatment due to partial conversion of the phase of MoS2.112 In this case, the atomic arrangement of 2H phase gradually
3.3.3. Phase Transition by Laser and e-Beam transformed to 1T phase, as shown in Figure 7d. These
Irradiation. There are other fascinating approaches for technique may offer pattern-able phase transition in future,
phase engineering of LTMdCs. Unlike Li intercalation, no which could be extended to industrial applications.
chemical treatment is necessary for laser or e-beam induced
phase transition in LTMdCs. Recent study showed a route to 4. ELECTRONIC STRUCTURES
fabricate ohmic homojunction contact by laser-induced phase
transition in MoTe2 with thinning process.10 The techniques 4.1. Electronic Structures of Representative Metallic
have previously been reported for thinning the layered Layered Transition Metal Dichalcogenides
materials in graphene and MoS2.159−162 Figure 7c shows the Electrons form discrete energy levels in atoms. Electrons in
schematic of laser-induced phase transition. Laser irradiation molecules form a series of new electronic energy levels via the
generates local heat in 2H-MoTe2. Because of the small energy hybridization of orbitals, grouped as bonding (occupied) and
difference between 2H and 1T′ phases in MoTe2, the antibonding (unoccupied) levels.163 Solids consist of a huge
irradiated site in 2H-MoTe2 changed to 1T′, forming an number of atoms, which generates a collection of discrete
ohmic contact. The fabricated MoTe2 transistor with energy levels with small energy differences between them.
homojunction exhibits the improvement of the carrier mobility These energy levels can be grouped into conduction and
by a factor of 50 with an on/off ratio as high as 106. Phase valence bands, similar to the unoccupied and occupied energy
transition from 2H to 1T was established in Re doped MoS2 levels in molecules, respectively. If the atoms are arranged in an
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Table 5. Growth Conditions for the Monolayer m-LTMdCs by Various CVD Processesa
experimental conditions for monolayer
metals chalcogens ref type source temperature (°C) shape
Ti Se 58 MBE Ti metal 220
57 MBE Ti metal 200−300
59 MBE Ti metal 450

Zr S 69 MHCVD ZrCl4 600−900 SC flake

70 MHCVD ZrCl4 730−830 SC flake

Nb Se 80 MBE Nb metal 325

81 MBE Nb metal 450−780 SC flake

Ta S 96 MBE Ta metal SC flake

Pt Se 107 MBE Pt metal 200−270

106

Mo Te 125 LSCVD AHMb 610 SC flake

126 LSCVD AHM 700 SC flake
127 HCVD MoO3 and MoCl5 750−850 SC flake
128 MBE Mo metal 250−350
129 MBE Mo metal 25−350
130 MBE Mo metal 250−450

W Te 127 HCVD WO3 and WCl6 750−850 SC flake

136 LSCVD AMTc 650 SC flake
137,138 MBE W metal 250
a
Molecular beam epitaxy (MBE) is also included. SC is an acronym of single crystal. bAHM: ammonium heptamolybdate. cAMT: ammonium
metatungstate.

Figure 7. Other synthetic approaches. (a) Molecular beam epitaxy (MBE). Reproduced with permission from ref 81. Copyright 2016 AIP
Publishing. (b) Li-intercalation. Reprinted by permission from ref 145. Copyright 2014 Macmillan Publishers Ltd. (c) Phase transition by laser
irradiation. Reproduced with permission from ref 10. Copyright 2015 American Association for the Advancement of Science. (d) Phase transition
by e-beam exposure. Reprinted by permission from ref 113. Copyright 2014 Macmillan Publishers Ltd.

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Figure 8. Classification of band structures of materials in k-space. (a) metal, (b) semiconductor, and (c,d) semimetals.

order, a crystal is formed. In such a case, the electronic

structure can typically be described in the reciprocal or
momentum, space (e.g., k-space).163
Figure 8 shows the general electronic band structures of
materials in k-space with several different scenarios. If there is
no overlap between the conduction and the valence bands
(Figure 8a,b), which occurs when the number of electrons in
the primitive cell is even, a band gap exists between these two
bands, forming a semiconductor or insulator. The gap between
the two bands is called the energy band gap. The Fermi level is
located at the middle of the bandgap, in principle. If the
number of electrons in the primitive cell is odd, the material
becomes metallic because one energy band is partially
occupied. Another situation is when there is a small overlap
in the k-space between the conduction and valence band
(Figure 8c), such that the concept of the conduction band and
valence band is no longer clear anymore. In such a case, Figure 9. Relative energy levels of representative transition metals and
regardless of whether the number of electrons in the primitive chalcogen atoms. Reproduced with permission from ref 173.
cell is odd or even, the materials have metallic characteristics Copyright 1986 Springer.
with a large number of free electrons at the Fermi surface. If
the overlapped energy regime is small, these materials are The electron characteristics near the Fermi level of the
called semimetal with a low electron and hole concentrations LTMdCs are strongly determined by the interactions among
at the Fermi surface. These materials are interesting, having electrons in the p, s, and d orbitals of each species. The energy
two different types of carriers: electron- and hole-like carriers, level of the s orbital in chalcogen atoms is relatively deep in the
which give rise to a large magnetoresistance.164−166 The valence band and does not significantly contribute to the band
situation becomes more interesting when there is an structure near the Femi level.173 The group IVB transition
intersection between the conduction and valence bands metals such as Ti, Zr, and Hf have four electrons in their
(Figure 8d). Topological insulators and Weyl semimetals fall outershell, two for each in the d and s orbitals with a d2s2
into this category, which are discussed in the section 6.167−172 configuration. The most common phase of this group with
Because crystals are formed by a certain ordered arrange- chalcogens in LTMdCs is the 1T phase. Origin of such a 1T
ment of atoms, their electronic band structures are strongly phase is little known at the moment. The change in the band
correlated to their crystal structures (e.g., bond lengths, angles, structure of MX2 (M, metal; X, chalcogens) of group IV can be
and coordination) and the electronic configurations of the intuitively explained by considering the relative energy
constituent elements.173 The crystal structure of the material is difference between metals and chalcogens. Because the total
also determined by the electronic structures of the constituent number of valence electrons in the unit cell is 10, an even
elements. Although the prediction for the existence of number, this is likely to exhibit semiconducting property. In
compounds (e.g., chemical composition) and their structures fact, HfS2, HfSe2, ZrS2, ZrSe2, and TiS2 are semiconduc-
is still challenging from the theoretical point of view, tors.32,173 The energy level of the d orbital increases from Ti to
understanding the electronic energy of elements is a crucial Zr to Hf, which leads to a larger energy difference from the
step to build an intuitive picture of the properties of crystals. energy level of p orbital of chalcogens. Therefore, the bandgap
Figure 9 shows the relative energy levels of group IV, V, and VI between the conduction and valence bands increases, giving
transition metals compared to those of chalcogen atoms.173 rise to a larger bandgap in HfS2 (HfSe2) compared to that of
Chalcogen atoms have six valence electrons in the s and p ZrS2 (ZrSe2).174,175 Similarly, the band gap decreases when S is
orbitals (s2p4), while transition metals have a wide range of replaced by Se. Eventually, semimetals are formed in Te
electron configurations with the outermost electrons mainly compounds.173−176 TiSe2 is presumably similar to a semi-
located at d and s orbitals. conductor. However, the energy levels of the Ti d orbital and
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Figure 10. (a) Calculated and (b) experimental ARPES of TiS2 and (c) the Fermi surface. Reproduced with permission from ref 187. Copyright
2015 Institute of Physics Publishing. (d) Calculated and (e,f) experimental ARPES of TiSe2. Reproduced with permission from ref 186. Copyright
2017 Elsevier.

Figure 11. (a) Hexagonal Brilluoin zone (b,c) low and (d,e) high resolution ARPES band structure of VSe2. (f−j) The Fermi surface slices of
selected BZ planes. Reproduced with permission from ref 189. Copyright 2012 American Physical Society.

Se p orbital are very close to each other, leading to an overlap d5s1, which is the half-filled configuration. In contrast, the most
in the energy to form a semimetallic phase. We discuss the stable form in W is d4s2. However, it is worth mentioning that
band structure of TiX2 later in this review. the d5s1 configuration has a similar energy to d4s2 configuration
The LTMdCs formed by the group VB transition metals are in W.173 CrX2 is a metastable phase with a 1T structure, which
always metallic due to the presence of odd number of electrons does not appear in the equilibrium phase diagram of Cr-X.178
in their orbitals.173,177 VX2 is stable with a 1T phase, while In contrast, WX2 and MoX2 share a common 2H stable phase
both NbX2 and TaX2 have 2H phase. The 1T phases are stable with semiconductor characteristics at room temperature,
at only high temperature.177 Instead, at room temperature, excluding WTe2, which has a Td structure.31 The MoTe2
they transform to distorted phases. A lower symmetry structure reveals a T′ (a distorted form of Td) phase at high
belonging to the space group 12 of MTe2 is also observed in temperature.8 The T′ phase can transform to the Td phase
this group. and vice versa by controlling the Te vacancy, temperature, or
The group VIB transition metals have six valence electrons. pressure.179 The metallic phases of WTe2 and MoTe2 are
The most stable electron configuration of both Cr and Mo is covered in the next section.
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Figure 12. Band structure of 2H-NbSe2 and 1T-NbSe2. Reprinted with permission from ref 190. Copyright 2016 Macmillan Publishers Ltd.

4.1.1. 1T-TiS2 and 1T-TiSe2. The fundamental band There is a phase transition from 1T phase to its distorted phase
structure of the bulk TiS2 and TiSe2 were undefined for a long that is stable at room temperature.177 Therefore, to determine
time.173 This is because the experimental band structures the band structure of the 1T phase, measurements should be
cannot be easily obtained from the whole k-space; moreover, performed at high temperatures. The band structure we discuss
the simulation method for the band structure calculation here is not that of the 1T phase but of its distorted phases.
usually underestimates the material bandgap.180−185 The band Figure 12 shows the band structure of a mixture of the 2H and
structures of bulk TiS2 and TiSe2 have recently been defined 1T phases at 40 K, where the distorted phase of the 1T
with the B3LYP hybrid functional, the MBJ potential, and a structure has been formed.190 The mixed sample of 1T and 2H
well-developed ARPES technique. Figure 10 shows the phases is synthesized by annealing the coevaporation film of
calculated and experimental band structures of 1T-TiS2 and Nb and Se atoms on bilayer graphene/6H-SiC (0001) at 530
1T-TiSe2.186,187 In TiS2, there is no overlap between the °C. Compared to the bulk 2H phase (Figure 12b), several
conduction and valence band. Therefore, TiS2 is a semi- additional bands appear, denoted as the band structure of 1T
conductor with a small indirect band gap of 0.53 eV, where the phase with a red curve (Figure 12a). Interestingly, the flat band
maximum (minimum) of the valence (conduction) band is (α band) does not match with the DFT simulation for 1T
located at the Γ point (M point). The simulation and phase, indicating the Mott−Hubbard band in the Mott
experimental data are quite consistent, although a smaller gap insulator phase.190 This implies that the distorted phase
(0.4 eV) is predicted from the simulation result, as shown in reveals the Mott insulator in the 1T phase structure. We
Figures 10a,b.187 A small electron pocket in the conduction discuss this in detail in the PLD section.
band emerges at the M point due to the n-doping effect of the 4.1.4. 1T-, 2H-, and 4H-TaS2. In addition to the structural
S vacancies, which are formed during the crystal growth, differentiations between compounds with the same chemical
leading to six Fermi contours at the M points, as shown in composition, an interesting feature of LTMdCs is the
Figure 10c. In contrast to TiS2, a small overlap between the formation of different stacking sequences along the c-
valence and conduction bands between Γ, A. and L points direction.173 TaS2 displays both 1T and 2H structures. The
appears in TiSe2 (Figures 10d−f). As a consequence, TiSe2 is a 4H polytype is a combination of the 1T and 2H phases, which
semimetal with an electron pocket near the L point and a hole has four layers, two layers each of the 1T and 2H
pocket at the Γ point.186 structure.173,33−41 Therefore, the band structure and properties
4.1.2. 1T-VSe2. Vanadium belongs to group VB in the of 4H phase are a mixture of those of the 1T and 2H
periodic table. There is one more electron in the unit cell of phases.33,35−41,173,191 The band structures of 2H-, 1T-, and 4H-
1T-VSe2 compared to 1T-TiSe2. Therefore, it is obvious that TaS2 are shown in Figure 13. The Fermi level cuts through the
1T-VSe2 is metallic with a partially filled band.173,188,189 Figure two (one) bands in 2H (1T) phase with two (one) layers in
11 shows the band structure and Fermi surface of VSe2 the unit cell. In the 4H structure, there are four bands, two
from 1T and two from 2H. The two types of bands intersect
measured by ARPES with the soft X-ray at 10 K.189 It is
along the M−K direction. The interaction between these bands
clear that the Fermi level crosses the band along the Γ−K
lead to new properties of the 4H phase, which do not appear in
direction (Figure 11e), indicating the metallic nature of VSe2.
the 1T and 2H phases. However, the 4H phase as yet remains
Along the z direction (Γ−A), the band dispersion is smaller
elusive.
than that in the in-plane directions (Γ−M and Γ−K). There
are two relative flat bands with small dispersion, one is near the 4.2. Layer Dependence of the Band Structure in Metallic
Fermi level and another is approximately 2 eV below the Fermi Layered Transition Metal Dichalcogenides
level. The Fermi surface of VSe2 is a closed surface with six Although the interaction between the layers in LTMdCs is the
loops. Parts f and g of Figure 11 show the calculated and weak van der Waals force, this interaction still plays an
experimental Fermi surface in different planes. The theoretical important role to construct the band structures and properties
simulation agrees well with the experimental data. of LTMdCs as well as 2D materials.192−196 An obvious piece of
4.1.3. 1T- and 2H-NbSe2. Although Nb belongs to group evidence is that the band dispersion along Γ to A of many
VB similar to V, NbSe2 has two crystal structures, 1T and 2H bands is still not negligible.23,197,198 As a consequence, the
phases.173,177 Both of these are metallic because of the odd band structures of LTMdCs are strongly dependent on the
number of valence electrons in Nb. However, the 1T phase is number of layers. Figure 14 shows the band structure of TiSe2
not the most stable phase of NbSe2 at room temperature.177 from monolayer to six-layer samples of the normal and CDW
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5. PERIODIC LATTICE DISTORTION OR CHARGE

DENSITY WAVE IN MATALLIC LAYERED
TRANSITION METAL DICHALCOGENIDES
5.1. Periodic Lattice Distortion Phenomenon
In many metals, the phase with the primitive cell structure
(called the normal phase) is unstable when the temperature is
lowered.177,202−206 Their structures distort to form new
structural phases, known as the periodic lattice distortion
(PLD) phase (or the charge density wave (CDW) phase).206
The name CDW does not clearly reveal the physical intuition
of the distorted phase because the waveform of the charge
density originating from the periodic arrangement of atoms
does exist even in the normal phase.202,203 Therefore, we prefer
to use the name PLD rather than CDW in this review. The
phenomenon of PLD occurs in many 2D layered metallic
materials.177 The temperatures of the PLD transitions have a
wide range, differing between materials.177 Additionally, one
material can have many different transitions. The structure of
the PLD phase can be commensurate (C) or incommensurate
(IC) with the normal structure. Figure 16a shows the distorted
structure of TaS2 at a low temperature. The size of the unit cell
in the C-PLD phase is 13 × 13 of the normal phase, as
shown in Figure 16a.177 In TaS2, there are three transitions:
from the normal phase to the IC phase at 543 K, from the IC
to the nearly commensurate (NC) phase at 353 K, and from
the NC to the C phase at 190 K.177 The schematic
corresponding to each phase transition is summarized in
Figure 16b.92 The position of the atoms in the PLD phase is
slightly distorted from the original position, which can be
revealed from TEM and scanning tunneling microscope
(STM) observations (Figure 16c−e).207,208 It is worth noticing
Figure 13. Band structure of (a) 2H-, (b) 1T-, and (c) 4H-phase of that the amplitude of the distortion is very small (∼0.1 Å)
TaS2. Reproduced with permission from ref 173. Copyright 1986 compared to that of the normal structural phase transition,
Springer. which generates a completely different crystal structure. The
PLD transition is always accompanied by a softening phonon,
called the lattice instability, which is discussed further in the
next section.177
phases.194 With the few layers, the Γ (M) and A (L) points are Figure 17 shows another example of the PLD transition in
same. The overlapping between the top valence and bottom TiSe2.210−212 There is only a transition at 200 K from the
conduction bands at Γ and M points increases as the number normal phase to the distorted one with 2 × 2 × 2 structure.
of layers increases for both the normal and CDW phases. Interestingly, TiSe2 has domains with different chiralities
Consequently, a large band overlap is clearly shown between (clockwise and anticlockwise) in the PLD.211 The formation of
the A and L points in bulk. The interlayer interaction becomes these different domain structures can be understood by relying
more dominant in group VIIIB (Ni, Pd, Pt). The metallic on the distorted structure of Se on the top and bottom layers
nature of the bulk can transform to semiconducting character- in the 2 × 2 × 2 lattice. Along with the in-plane distorted
istics in the few layer sample.199 Figure 15 shows the band structure, there is relative movement of Se atoms on the top
structures of mono and bilayer PdS2. While bilayer PdS2 is a and bottom layers, marked with red and blue arrows,
semimetal, the monolayer is a semiconductor with a bandgap respectively.210 It can be seen that the directions of top and
of 1.1 eV. This phenomenon is caused by the strong vdW bottom layers are opposite, one is clockwise and another is
interlayer interaction, which makes the conduction band more anticlockwise. The roles of the top and bottom layers is
dispersed, overlapped with the valence band, implying the interchangeable, giving rise to domains with different chiralities
semimetallic or metallic behavior. The phenomenon occurs in in real space (as shown in Figure 17d).211
other type of layered materials such as GeP3 and antimonene
(Sb) and is expected to reveal in other layer materials with a 5.2. Mechanism for Periodic Lattice Distortion Transition
strong vdW interaction.200,201 This interesting phenomenon The instability of a one-dimensional metal at low temperature
could lead to the design of a metal−semiconductor contact was first proposed by Rudolf Peierls.202,203 Because of its
without any physical boundaries.199 intuitive and simple nature, the Peierls model is typically used
In addition to the variation of band gaps or the types of band to explain the PLD transition in many text books and is a good
structures (metal or semiconductor), many other properties starting point before going to the introduction of a
can be changed when decreasing the thickness of materials complicated microscopic theory. We explain here why this
such as the PLD, magnetism, and superconductivity. We will simple model is not applicable in many cases when studying
discuss these issues in the next chapters. real 2D materials. Figure 18a shows the band structure of one
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Figure 14. Layer-dependent band structure of TiSe2 from monolayer to six layers. (a) Normal phase, (b) periodic lattice distortion (PLD) wave
phase, and (c) simulated band structure of normal and PLD phases. Reproduced with permission from ref 194. Copyright 2016 American Chemical
Society.

unoccupied states (more precisely, the electrons are redis-

tributed to states both below and above the Fermi level,
following the Fermi−Dirac distribution), which has higher
energies than the unoccupied states in the normal phase.206 As
a consequence, the energy difference in the distorted phase
compared to the normal phase is reduced when the
temperature is increased, leading to a transition to the normal
phase at high temperatures.
Why does the distortion take place at 2a and not at 3a or 4a?
Assuming the distortion happens at 3a, the gap will form at the
π
± 3a position, located below the Fermi level. Both the lower
and higher energy states are occupied, and hence, no energy
gain is obtained in this case. This is the reason why it is
believed that the PLD transition is always accompanied by a
metal−insulator transition, with the gap opening at the Fermi
level.202,203 However, this situation is only applicable for a one-
band model. In real materials, the electronic band of the
Figure 15. Band structure and density of states of mono- and bilayer normal phase is degenerate. A small distortion will differentiate
PdS2. Reproduced with permission from ref 199. Copyright 2016 John the degeneracy of this band, and the energy change can be not
Wiley & Sons. the same as that of one band. In many cases, the total energy
distribution of electrons to this band will lower the energy as
electron model of a 1D periodic potential with a lattice shown in the right panel of Figure 18c without any formation
constant a in the first Brillouin zone.202,203,206 In this model, of a band gap at the Fermi level.
the electronic band is half-filled, which indicates that the Fermi Figure 19 shows two different cases for the PLD phases of
π
level intersecting the band at ± 2a . However, this metallic band TiSe2 and 1T-TaS2, where the energy gap is generated below
and at the Fermi level, respectively.58,209 In TiSe2, the PLD
is not the minimum energy structure. If the structure is slightly phase have 2 × 2 × 2 supercell, and their Brillouin zone (red)
distorted, forming a periodic potential with 2a, the band is smaller than that of the normal phase (blue) (Figure 19a).
π
structure will have a gap at the position ± 2a at the Fermi level, The M point of the normal phase is folded to the Γ point of
as shown in Figure 18b. Because the occupied states, which the PLD phase. As a consequence, the electron band of the
locate below the Fermi level, have lower energy compared to normal phase at the M point appears at the Γ point in the PLD
those of the undistorted phase, the distorted structure is more phase, which is clearly shown in Figure 19b. The electronic
stable than the normal structure. At higher temperatures, the band at the Γ and M points are lower in the PLD phase
electrons below the Fermi level will be thermally excited to the compared to the normal phase, indicating a reduction of the
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Figure 16. Periodic lattice distortion in 1T-TaS2. (a) The schematic of the relative movement of the commensurate PLD phase compared to the
normal phase. Reprinted with permission from ref 209. Copyright 2015 Macmillan Publishers Ltd. (b) Schematic of formation of different
transition phase in 1T-TaS2. Reproduced with permission from ref 92. Copyright 2015 American Association for the Advancement of Science. (c,d)
The TEM image of the C-PLD phase, which clearly reveals the star shape of the C-PLD phase. Reprinted by permission from ref 208. Copyright
2010 Macmillan Publishers Ltd. (e) STM image of the C-PLD phase. Reproduced with permission from ref 207. Copyright 2016 Cornell
University Library.

electronic energy. A similar trend is also observed at the L gives rise to the concept of Fermi surface nesting, where the
point.186,210 In fact, no gap is formed at the Fermi level. Many electron screening suddenly changes in q space. The physical
similar examples can be found in other materials such as 2H- quantity directly related to Fermi surface nesting is the bare
NbSe2 and 2H-TaS2.210,213 It is noticed that the proposed electronic susceptibility, expressed by213
excitonic mechanism in TiSe2 is not suitable for this case
f 0 (En0′ k − q) − f 0 (Enk
0
)
because all changes in the band structure occurs below the X 0(q) ∼ 2 ∑ ∑ 0
Fermi level.214,215 The time-resolved X-ray spectroscopy also nn′ k
Enk − En0′ k − q
excludes the excitonic mechanism.216
Figure 19c shows the experimental (left) and calculated This quantity is only dependent on the Fermi surface and
(right) band structures of the C-PLD phase of 1T-TaS2. In temperature. As mentioned above, the PLD can occur without
contrast with the TiSe2 case, a gap is generated in the C-PLD a gap opening at the Fermi level in real materials. In such cases,
phase of 1T-TaS2 along all in-plane directions, although there the concept of Fermi surface nesting has a completely
is still an electronic band intersecting the Fermi level along the unphysical meaning and hence cannot be used to represent
the PLD transition. Even with the case of the gap opening,
Γ−A direction,.209 In addition, the 1T-TaS2 is a strong
there are too many distinguishing features between the Kohn
electron-correlated system and the Mott transition is proposed
anomaly and PLD transition.213 One representative difference
to explain the PLD formation.208,217 However, a softening of is that the energy gain due to the Peierls distortion is
the phonon modes does reveal in the DFT simulation without contributed from the energy spanning across a wide range of k-
consideration of the strong correlation effects, indicating the space, while the Kohn anomaly sharply occurs at a specific k-
significant effect of the variation of electronic energy following point. Therefore, we do believe that the concept of Fermi
the lattice distortion, named electron−phonon cou- surface nesting should be used carefully for explaining the PLD
pling.218−220 The general driving mechanism to minimize the transition, as clarified below.
electronic energy in both cases is similar to the Jahn−Teller To study the phase transition, a macroscopic theory based
effect in chemistry.221 on the free energy should be considered. The theory of
It is worth mentioning the concept of the Kohn anomaly electronic free energy for the explanation of the PLD phase
together with Fermi surface nesting and how these correlate to transition has been developed for several decades.177 In this
the Peierls distortion. The Kohn anomaly is a phenomenon, approach, the energy of the distorted phase can be expressed
wherein the phonon spectrum is softened due to the reduction by
of electron screening at a certain k-point.222 In the 1D model,
F = F0 + ΔF
the softening of phonon occurs at q = 2kF. The softening of the
phonon due to the Kohn anomaly is consistent with the where F0 is the energy of the normal phase and ΔF is the
instability of the one-electron model in Peierls distortion that energy change due to the distortion. This ΔF is dependent on
generates the 2a supercell of the PLD phase.31,202,203,210 This the q vector and phonon mode λ, expressed by
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Figure 17. Formation of the PLD domain in TiSe2. (a−c) STM and corresponding fast-Fourier transform images of the distortion phase of TiSe2.
(d,e) Explanation of the chiral domain formation in TiSe2. The relative movement of Ti (cyan) and Se (yellow) compared to the normal phase.
The red (blue) arrows indicate the distortion of the top (bottom) layer. The movement of the top and bottom layers is interchangeable, which can
happen in the same layer but in a different area in real space, giving rise to the formation of chiral domains. Reproduced with permission from refs
211 and 210. Copyright 2010 and 2015 American Physical Society, respectively.

Figure 18. (a−c) 1D Peierls distortion.202 (d) Extended model for multiband model that typically happens in real materials.

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Figure 19. (a,b) Band structure of the distortion phase of TiSe2. The band of the Γ point of the normal phase is folded into the M point in the
distortion phase. No band gap is generated at the Fermi level. The energy level at the Γ and M points decreases. Reprinted with permission from ref
58. Copyright 2015 Macmillan Publishers Ltd. (c) Experimental ARPES (left) and DFT simulation (right) band structures of 1T-TaS2. Reprinted
with permission from ref 209. Copyright 2015 Macmillan Publishers Ltd.

1 1 The PLD transition is always accompanied by the softening

ΔFqλ = − χ (qλ)|Q qλ|2 + D2(qλ)|Q qλ|2
2 2 of at least one phonon mode at a certain q point.177 This
characteristic can be measured by inelastic scattering, which
The first factor is related to the electronic change and the
second term related the elastic distorted energy due to the can directly observe the phonon spectrum of materials.223,224
distortion. Parameter χ(qλ) is called the generalized electronic Figure 20a shows the experimental phonon dispersion of 2H-
susceptibility: NbSe2, which clearly reveals the softening of the acoustic
phonon mode when the temperature is lowered to the
f 0 (En0′ k − q) − f 0 (Enk
0
) transition temperature, 33 K.223 The energy of the phonon is
X 0(q) = 2 ∑ ∑ 0
nn′ k Enk − En0′ k − q completely zero at this temperature, indicating the PLD
transition. At a lower temperature, the phonon mode appears
|V1λ(nk , n′k − q)|2
again, which is the phonon mode of the new PLD phase. The
where Vλ1 is a factor relating to the k and q vector electron− PLD transition of TiSe2 can be detected by X-ray thermal
phonon coupling strength. If Vλ1 is not dependent on the k and diffuse scattering.224 The intensity of the measurement at the
q vectors, the generalized electronic susceptibility is propor- L-point suddenly increased when the temperature reaches to
tional to the bare electronic susceptibility: 190 K, indicating the transition from the PLD phase to the
normal phase. This phonon softening can also be revealed in
f 0 (En0′ k − q) − f 0 (Enk
0
)
X 0(q) ∼ 2 ∑ ∑ the theoretical DFT simulation.225 It is notable that the
0
nn′ k
Enk − En0′ k − q electronic temperature describing the thermal excitation of the
electrons can be included in the total free energy calculation.
It is clear that the concept of bare electronic susceptibility This factor is known as the smearing factor, which is normally
concept can only be applied to study the PLD transition where
Vλ1 is k- and q-independent, which is not easily satisfied in real used for a convergence of the numerical issue in DFT. The
materials. This condition may take place easier in 1D materials, phonon spectrum of the normal phase dramatically changes
where the nesting concept has been changed to imperfect with the smearing value. This is clearly shown in 2H-NbSe2,
nesting concept.205 TiSe2, and other PLD materials.223,225
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Figure 20. (a) Evolution of phonon dispersion with temperature in 2H-NbSe2. A softening of the acoustic phonon mode is clearly revealed.
Reproduced with permission from ref 223. Copyright 2011 American Physical Society. (b) The evolution of the X-ray thermal diffuse scattering
intensity of TiSe2 with temperature along the A−L−A line with coarse and fine scans (inset), which shows a strong Bragg peak below 190 K.
Reproduced with permission from ref 224. Copyright 2001 American Physical Society. (c,d) The simulated phonon dispersion of (c) 2H-NbSe2.
Reproduced with permission from ref 223. Copyright 2011 American Physical Society. (d) TiSe2. Reproduced with permission from ref 210.
Copyright 2015 American Physical Society.

Figure 21. Evolution of resistance with temperature in (a) TiSe2. Reproduced with permission from ref 232. Copyright 2017 American Chemical
Society. (b) 1T-TaS2. Reprinted by permission from ref 234. Copyright 2014 Macmillan Publishers Ltd.

5.3. Experimental Characterization of Periodic Lattice the resistance, the transition in TaS2 is very sharp with a huge
Distortion hysteresis. In TiSe2, it is necessary to take the derivative of the
In addition to the direct structure characterizations such as R−T curve to determine the transition temperature, which is
STM or XRD and TEM, the PLD transition can also be approximately 200 K. The transition of TaS2 is clearly shown
detected by indirect methods such as electronic transport and in the R−T curve at 353 and 230 K, consistent with the XRD
Raman scattering.226−234 Although there is no common feature and STM studies. The different behaviors between TiSe2 and
among different materials, the characteristic of the resistance TaS2 may be explained by the different characteristics at the
with temperature (R−T curve) shows an abnormal metallic Fermi level in band structure of the PLD phase as mentioned
behavior.227,232,234 Figure 21 shows the R−T curves of TiSe2 earlier. The hysteresis is typically represented for a metal−
and TaS2.232,234 While the TiSe2 shows a smoothly change of insulator transition.
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Figure 22. (a,b) Evolution of Raman spectroscopy in 2H-NbSe2. (c−e) Evolution of Raman spectroscopy in 1T-TaS2. Reprinted by permission
from ref 233. Copyright 2015 Macmillan Publishers Ltd. Reproduced with permission from ref 227. Copyright 2016 American Physical Society.

When the transition to the PLD phase occurs, the distortion transition. For almost 2D metallic systems, it is widely
reduces the symmetry of the materials, giving rise to new active accepted that the Bardeen−Cooper−Schrieffer (BCS) super-
Raman modes. By monitoring the appearance of these peaks, conducting theory covers the physics behind this.235,236 Both
the phase transition can be determined.227,228,232,233 Figure 22 BCS superconductivity and PLD transitions are related to
shows the evolution of Raman spectra of 2H-NbSe2 and 1T- phonons, and their interactions with electrons.237−241 There-
TaS2 with temperature changes.227,233 The appearance of new fore, the study of the phonon spectra of the 2D metallic
peaks near 30 and 200 cm−1 in 2H-NbSe2 are clearly observed systems contains rich physics related to superconductivity and
during cooling down. The corresponding intensities of the PLD via phonon−electron coupling.
softened peak are collected in the Figure 22b with different There are two approaches for tuning PLD transition and
sample thicknesses. The transition temperature can be BCS superconducting phase: to control the carrier density by
extrapolated from on the change in the peak intensity. The doping or to use pressure.230,242 Figure 23a shows the
Tc is clearly incremented when the thickness of the sample is magnetic susceptibility of Cu-doped TiSe2, which exhibits a
reduced. This method is rather difficult in experiments because drop near the PLD transition. The transition occurs at a lower
a strong intensity of the Raman peak is required to reduce the temperature with increasing the Cu content. The resistivity
error during extrapolation. Another approach based on the also reveals the same trend up to 0.6% Cu. At 0.6% Cu, the
peak position is more accurate determination of Tc, as proved superconductivity appears with a resistance drop at 2 K. The
in the cases of TiSe2 and TaS2.227,232 In this approach, some critical temperature, Tc, increases further with increasing
Raman peaks even in the normal phase show a nonmonotonic dopant concentration and reaches the maximum transition
variation. The Tc of TaS2 for the C-PLD transition was temperature at 4 K with 8% Cu. These behaviors of PLD and
determined to be 140 and 21 K by decreasing and increasing superconductivity also emerges by applying pressure, as shown
the temperature, respectively. This is consistent with the in Figure 23c.230 Figure 23d summarizes the dome shape of
transport measurement. TiSe2 by tuning the dopant and pressure. The doping has a
stronger effect compared to that of pressure in this case. It is
5.4. Tuning Periodic Lattice Distortion Transition and interesting to see how the phonon changes when the PLD is
Superconductivity Phase Formation
suppressed. Figure 24 shows the evolution of the Raman
In addition to the interesting physics behind the PLD spectrum, measured at 3.5 K, with pressure.228 The Eg (70
transition, this transition occurs in many systems and can be cm−1) and A1g (110−140 cm−1) modes of the PLD phase are
tuned to display superconductivity. The common “super- suppressed with increasing pressure, indicating a melting of the
conductivity dome” shape, which happens in all types of PLD transition. Although the simulation data of the phonon
superconductors, does reveal in materials showing the PLD spectrum of TiSe2 by density functional perturbation theory
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Figure 23. (a,b) Magnetic susceptibility and resistivity of Cu-doped TiSe2 at different temperature. Reprinted with permission from ref 242.
Copyright 2006 Macmillan Publishers Ltd. (c) Resistivity of TiSe2 under different pressures and temperatures. (d) Superconductor dome shape of
TiSe2. Reproduced with permission from ref 230. Copyright 2009 American Physical Society.

Figure 24. (a) Evolution of the Raman spectrum of TiSe2 at 4 K under different pressures. Reproduced with permission from ref 228. Copyright
2003 American Physical Society. (b) Calculated phonon dispersion of TiSe2 at 5 GPa. The softened phonon mode is still reserved but maintains
real at low electronic temperature, indicating the suppression of the distortion phase. Reproduced with permission from ref 210. Copyright 2015
American Physical Society.

also shows the softening mode at the L and M points, the real phase but not as strong as in TiSe2.243 As shown in Figure 25,
value is maintained, implying the stability of the normal state at the PLD transition is strongly tuned while the super-
low temperatures.225 Similar effects of pressure are also conductivity transition is unaffected. This can be explained
observed in 2H-TaS2 and 2H-TaSe2, however, the situation by considering the coupling of these two-phase transitions with
is different in 2H-NbSe2. Some degree of correlation is the phonon. While the PLD is strongly coupled with the
observed between the PLD state and the superconducting longitudinal acoustic mode, the superconductivity state is
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state has a tendency to be suppressed in the thin samples with

a reduction of the transition temperature.234,244 The carrier
concentrations of the metallic state can be controlled by
external doping methods with few layer samples such as the
common oxide gate structure and surface doping by molecules.
Figure 27a shows the phase diagram of 1T-TaS2 with different
gate bias, which controls the carrier density of the sample.234
At low temperatures, a clear transition from the C-PLD to the
NC-PLD and to the SC phase can be seen with increasing the
gate bias. The superconducting phase disappears when a higher
bias is applied, again forming a superconducting dome shape.
The similar trend is observed in TiSe2 (Figure 27b).246 This
approach is much advantageous for investigating the carrier-
dependent properties compared to the normal bulk approach,
in which the strong interaction forming the new bonding state
is difficult to exclude.
Figure 25. Superconducting dome in NbSe2. A weak correlation
between the PLD and superconducting phase is shown. Reproduced 6. OTHER PROPERTIES
with permission from ref 243. Copyright 2015 American Physical
Society. 6.1. Magnetism in 2D Metallic Layered Transition Metal
Dichalcogenides
strongly coupled with both the longitudinal acoustic mode and
the optical phonon modes.243 This is the difference compared 6.1.1. Magnetism in 2D Materials and Magnetic
to TiSe2, in which the both quantum phases are coupled with Metallic Layered Transition Metal Dichalcogenides.
the same acoustic phonon.236 The absence of 2D magnetic material has been predicted
An important property of 2D m-LTMDs is that the number from the 2D isotropic Heisenberg model by Mermin−Wagner
of layers can be controlled by a simple scotch tape theorem. However,247 magnetically ordered states such as
method.232−234,244,245 The thickness-dependent properties are ferromagnetism (FM) and antiferromagnetism (AFM) have
also interesting for the study of the quantum phase at the 2D recently been discovered in monolayer 2D materials such as
limit. This approach have been researched for a long time, semiconducting FM CrI3, semiconducting AFM MPS3 family
showing that the superconducting transition temperature is (M is Ni, Fe, Mn), and metallic FM GdAu2.192,248,249 2D
reduced when the thickness of 2H-NbSe2 decreases.245 magnetic materials have a number of advantages. Most van der
However, the PLD phase is stabilized at higher temperature Waals magnets have an intrinsic magnetocrystalline anisotropy
when the thickness of the sample is decreased, as shown in owing to the reduced crystal symmetry, which is a promising
Figure 26a. This trend is inverted in 1T-TaS2, where the PLD candidate for future spintronic materials.

Figure 26. Effect of thickness on the PLD and superconducting phase transitions in (a) 2H-NbSe2 and (b,c) 1T-TaS2. Reprinted by permission
from refs 233 and 244. Copyright 2015 Macmillan Publishers Ltd.

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Figure 27. Gate-controlled phase transitions in (a) 1T-TaS2 and (b) TiSe2. Reprinted with permission from refs 244 and 246. Copyright 2015
Macmillan Publishers Ltd.

Table 6. List of Magnetic LTMdCs (MX2) Materials with Basic Magnetic Propertiesa
materials space group experimental or theory structure magnetic ordering Tc or Nc (magnetic moment)
VS2 P3̅m1 experimental thin flake FM RT (0.51 μB/V atom)
VSe2 P3̅m1 theory monolayer FM 514 K (0.68 μB/V atom)
VTe2 P3̅m1 experimental bulk AFM 410 K (−)
CrS2 P3̅m1 theory bulk FM
CrSe2 P3̅m1 theory bulk AFM ∼550 K (−)
CrTe2 P3̅m1 theory bulk FM
CoS2 Pa3̅ experimental bulk FM 120 K (0.84 μB/Co atom)
CoSe2 Pa3̅ experimental bulk FM 50 K (8.4 μB/g)
FeS2 P3̅m1 theory monolayer FM 144 K (−)
FeTe2 Pnn2 experimental thin flake FM RT (−)
a
Tc (TN) indicates Curie (Néel) temperature.

A list of m-TMdCs in Table 6 provides information on ization versus magnetic field curves for thin VS2 and bulk VS2·
magnetic properties such as type of magnetic ordering, Curie NH3 are shown in Figure 28b. Both the thin and bulk VS2
(Néel) temperature, and magnetic moment. It should be noted show paramagnetic behavior in the high magnetic field region,
that some of TMdCs are not layered structures, although they while only thin VS2 shows hysteresis in the low field region,
are in a form of MX2 such as CoS2 and FeS2. Among the which is one of the main clues for ferromagnetism (zoomed
TMdC materials listed in Table 1, only monolayer vanadium graph in the inset of Figure 28b). Figure 28c shows a clear
dichalcogenides (VX2 where X = S, Se, and Te) are magnetic saturation of magnetization after subtracting signal from
layered materials. Although chromium dichalcogenides (CrX2) paramagnetic background. The trend of decreasing in the
are also layered structures, they are metastable and mainly exist saturated magnetization (Ms) and coercivity (Hc) with
as a stable form of Cr2X3 in nature. In this regard, we will increasing temperature further confirms the FM state in thin
mainly discuss on MX2 with the layered structures. VS2.
6.1.2. Ferromagnetism in Atomically Thin 2D Metallic Temperature dependence of magnetization for thin VS2
Layered Transition Metal Dichalcogenides (VS2 and nanosheets are shown in Figures 28d,e. The difference between
VSe2). Vanadium dichalcogenides (VX2) have been predicted zero-field cooling and field cooling at 100 Oe up to 330 K
as long-range FM ordered materials by first-principles indicates the existence of a magnetic state below 330 K, as
calculations even at monolayer thickness.43,250−253 The density shown in Figure 28d. Under the high magnetic field (8000 Oe)
of states and the atomic site projected density of states of VX2 (Figure. 28e), magnetic moment rapidly enhanced in the low
(VS2 and VSe2) are presented in Figure 28a. The difference temperature region (below 50 K) compared to the high
between the up and down spin states of VX2 indicates that
temperature above 50 K because the paramagnetic and FM
monolayer VX2 is a ferromagnetic material. The d states of V
signals are mixed. A fitted curve summing the T3/2 law Curie−
atoms are highly delocalized and hybridized with the p states of
Weiss law for the FM and the paramagnetic state is shown in
S and Se atoms, indicating covalent bonding between the V
Figure 28e, respectively, as described by the following
and X atoms. Ferromagnetism is mainly contributed by V
equation:
atoms, whereas X atoms contribute waekly to the total
magnetic moment. Parts b−d of Figure 28 display
M(T ) = Ms0(1 − AT 3/2) + CH /(T − θp)
experimental data from ultrathin VS2 flakes.43 The magnet-
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Figure 28. (a) Density of states for monolayer VS2 and VSe2. The magnetism mainly originates from the V atoms. Reproduced with permission
from ref 250. Copyright 2012 American Chemical Society. (b) Magnetization of thin and bulk VS2 (VS2·NH3) at room temperature, which shows a
hysteresis in the inset. (c) Paramagnetic signal-subtracted curves for thin VS2 at various temperatures. The inset shows the temperature dependence
of Ms and Hc. (d) Field cooling and zero field cooling curves for thin VS2. (e) Temperature dependence of magnetization of the thin VS2 fitted by
summing the FM and paramagnetic behavior. The inset shows zoomed curves from 250 to 350 K. (f) Magnetoresistance of thin VS2 as a function
of the magnetic field at room temperature. Reproduced with permission from ref 43. Copyright 2013 Royal Society of Chemistry.

where C is the Curie constant, θp is the paramagnetic Curie shows the magnetic hysteresis.256 This observation removes all
temperature, Ms0 is the saturated magnetization at 0 K, and A ambiguities of the chemical synthesis approach. It consolidates
is a structure-related coefficient.254,255 The extracted value of again the power of the theoretical prediction in 2D materials.
θp is negative sign (−6.6 K), indicating the coexistence of the Similar to VSe2, the 1T-TaS2 is predicted as a magnetic
AFM with FM phases.43 Thin VS2 also has a negative semiconductor in the PLD phase, which reveals that the
magnetoresistance of 6.5% at room temperature with a conduction and valence bands have different spin states.257
magnetic field parallel to the electrical current direction. The Figure 29 shows the band structure of bulk and monolayer
clear hysteresis in the magnetoresitance implies the FM TaS2 in the normal and PLD phases. In the normal phase, the
behavior of VS2 nanosheets (Figure 28f). band structure of monolayer TaS2 is similar to the in-plane
Although some experimental data show the magnetic band structure of the bulk TaS2. No significant change is
properties of VSe2, their origin is rather ambiguous. The observed, as shown in Figure 29a,b. However, the spin-
magnetic behavior might be induced by defect creation during polarized band appears in the monolayer of the PLD phase,
the synthesis process or substrate effect. However, the whereas the bulk prefers the no-spin state in Figure 29c,d. This
monolayer VSe2 growth by the MBE was recently demon- prediction has not yet been proven by experimental study, to
strated on the 2D substrate (e.g., graphite and MoS2), which date.
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Figure 29. Band structure of (a) bulk and (b) monolayer TaS2 in the normal phase and (c,d) PLD phase. Reproduced with permission from ref
257. Copyright 2014 American Physical Society.

Figure 30. (a) Calculated magnetic moment per V atom and X (S and Se) atom as a function of applied strain for monolayer VX2. (b) Energy
difference between the FM and AFM state of monolayer VX2 as a function of applied strain. Reproduced with permission from ref 250. Copyright
2012 American Chemical Society. (c,d) Magnetic moments of S (Se) (c) and Nb atoms (d) for monolayer NbS(Se)2 as a function of applied strain.
Reproduced withh permission from ref 267. Copyright 2012 American Chemical Society.

6.1.3. Strain Effect on Magnetism of Metallic Layered moments. This modulation of magnetic moment with strain
Transition Metal Dichalcogenides. Magnetism can be can be understood from the competition of ionic and covalent
efficiently modulated by strain in m-LTMdCs materials.258,259 bonding interactions between V and X atoms. For example,
When the 2D materials become ultrathin, they are flexible and when the tensile strain applied, the distance between V and X
can be easily elongated. Figure 30a shows the effect of in-plane atoms become elongated, resulting in the reduction of covalent
strain on magnetic moments per V atom (top panel) and per X bonding interaction but enhancement of the ionic bonding
atom (bottom panel) for monolayer 1T-VX2 from DFT interaction. Consequently, the enhanced ionic bonding
calculations.250 Tensile strain enhances both magnetic mo- interaction could lead to an increase in the population of
ments, whereas compressive strain quenches the magnetic unpaired electrons on V atom.
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Figure 31. (a) Atomic structures and calculated isosurfaces of spin density for monolayer VS2 with sulfur vacancies (Vno, V1s, V2s, and V3s).
Reproduced with permission from ref 271. Copyright 2016 Elsevier. (b) Atomic structures of pure, one side fully hydrogen passivated (1H) and
both sides fully hydrogen passivated (2H) monolayer VX2. (c) Calculated energy difference between FM and AFM states of monolayer VX2 in
terms of hydrogenation. Reproduced from ref 274. Copyright 2014 American Chemical Society. (d) Inverse field cooling magnetization curves of
Cr1−xVxSe2 samples at a magnetic field of over 0.1 T. The inset shows Curie−Weiss fitting in the low temperature region. (e) FC and ZFC curves of
Cr1−xTixSe2 samples at a magnetic field of over 0.1 T. Reproduced with permission from ref 278. Copyright 2013 American Physical Society.

Strain affects not only magnetic moment but also spin enhances further with higher strain. As discussed, the tensile
ordering. FM spin ordering state in VS2 monolayer is more strain can reduce the covalent bonding and enhance the ionic
stable than AFM state as the applied strain is modulated from bonding strength between Nb and X atoms. Accordingly, the
compressive to tensile strain (Figure 30b); a similar trend is enhanced ionic composition between atoms gives rise to
also observed in CrX2 system.250,260 This phenomenon of unpaired electrons and consequently the magnetic moment
magnetic ordering can be well explained by combining the can increase.265,266 Figures 30c,d show the magnetic moments
through-bond and through-space spin polarization mod- of NbX2 (X = S and Se) on Nb and X atoms with the variation
els.261,262 The FM state in monolayer VS2 could originate of strain.267
from through-bond spin polarization, where an a atom can 6.1.4. Doping Effect on Magnetism of Metallic
induce reverse spin on an adjacent b atom that is directly Layered Transition Metal Dichalcogenides by Vacancy,
bonded to another a atom. For example, the up-spin of a V Hydrogenation, and Substitution by Dopants. Doping or
atom induces down-spin to S atom. As a consequence, the alloying has been used for modifying material properties such
down-spin S atom again induces up-spin to another V atom, as carrier density, mechanical strength, and magnetism.268−270
leading to long-range magnetic ordering. Because the magnetic There are three main approaches for doping of LTMdCs:
moment of V atoms is greater than that of S atoms, the total vacancy creation, surface hydrogenation, and substitution by
magnetic moment is nonzero and leads to long-range FM dopants. Chalcogen vacancies have a significant influence on
ordering. Another magnetic ordering mechanism is the magnetic properties in LTMdCs. The structural schematic and
through-space model, where an a atom induces to reverse correlated isosurfaces of the spin density for four types of S
spin to an a atom without a mediation by a b atom. After all, vacancies (Vno, V1S, V2S, and V3S) are represented for
the through-bond and through-space interactions result in FM monolayer VS2 in Figure 31a.271 The spin density of V
and AFM state in magnetic materials, respectively. atoms adjacent to S vacancy is redistributed. The magnetic
Another interesting phenomenon is that strain even induces moments of V atoms near the S vacancy are gradually
magnetism to the nonmagnetic materials.263 NbX2 is a well- increased with more S vacancies (1.17, 1.67, 2.32, and 2.74 μB
known superconducting material, which has no magnetic for Vno, V1S, V2S, and V3S, respectively). The remaining
ordering.264 When the tensile strain is applied to monolayer electrons of the V atom adjacent to the S vacancy weaken the
NbX2, a finite value of magnetic moment is generated, which covalent bond between the V and S atoms to enhance the
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Figure 32. Schematic band structure of topological insulators (a) and Weyl semimetal (b) and their topological surface states. Fermi surface of type
I (c) and type II (d) Weyl semimetals with dot and electron−hole pocket shapes, respectively. Reproduced with permission from ref 167.
Copyright 2017 Annual Reviews.

magnetic moment of the V atom. The S vacancy can also alloying in the Cr−Se−Te system shows a tunable magnetic
change the magnetic ordering. FM ordering is stable in pristine ordering. For example, AFM is stable in the Se-based
VS2 (no S vacancy) whereas AFM ordering is stable with the compound, while FM is more favored in the Te-based
presence of S vacancies. compound.280−282
Hydrogenation of 2D materials can modify their magnetism 6.2. Weyl Semimetal in 1Td WTe2 and MoTe2
and induce FM from nonmagnetic materials.272,273 The
hydrogenation of monolayer VX2 is also estimated by DFT As mentioned in section 4, there is a case where the two bands
calculations. Figure 31b shows the representative structures of are crossed, known as band inversion.283−285 The name “band
pure monolayer VX2 and its one- (1H) and two-site (2H) inversion” comes from the energy difference between the two
hydrogen functionalization.274 The basic magnetic information energy bands changing from positive to negative in the
is summarized in Figure 31c. Two interesting features are momentum space. This phenomenon can generally happen in
presented: (i) the exchange energy (Eex), where Eex = (EAFM − the band structure of solids. In such a case, the interesting
EFM), of monolayer VX2 increases as the composition is varied physical concept of the topological band structure should be
from S to Te, indicating a higher Curie temperature; (ii) the considered, especially when these bands are inverted due to the
spin ordering and magnetic moment of VX2 are significantly spin−orbit coupling (SOC) effect.167,171,283−285 Figure 32
affected by hydrogenation. In the case of 1H, VX2 loses its shows the different behavior in the case of two bands
magnetic properties and further hydrogenation to 2H gives rise intersecting each other. In quantum mechanics, such
to AFM order in VX2. Hydrogen plays a role as an n-dopant to degeneracies (e.g., two states having the same energy at a
VX2, leading to the renormalization of the carrier density and certain k-point) should be not allowed due to the interaction
electronic structure, which highly influences magnetism. between the two bands.170−172,286,287 This phenomenon is
The substitution of the transition metals is one of the similar to that displays when bringing two similar atoms close
promising methods to induce magnetism to nonmagnetic together; their initial energy levels will split into two different
materials.275−277 CrSe2 has intrinsic AFM, and its magnetic energy levels. The consequence of the band−band interaction
ordering can be modified by V or Ti atom substitution.278 is the formation of an energy gap. This is the case of
Figure 31d shows the inverse magnetization of Cr1−xVxSe2; the topological insulator, as shown in Figure 32a.167 However,
high-temperature behavior follows a Curie law. The sign of the there are several special cases, where two band-crossing points
Curie constant is changed from positive to negative, which remain stable, as shown in Figure 32b.170,171 These points are
indicates that the AFM is generated as the concentration of called Weyl or Dirac points, depending on their degree of
substituted V atoms increases. No noticeable change from Ti degeneracy, owing to the nature of the linear behavior of these
atom substitution was observed below 20%, while over 20% Ti bands near the crossing points.170−172 It is worth noting that
substitution, the compounds displayed a FM behavior (Figure the linear band dispersion in topological insulator originates
31e). Ti substitution can elongate the lattice parameter a of from the surface state, while the 3D Weyl or Dirac points are
Cr1−xTexSe2 alloys and favors ferromagnetic interaction, which truly bulk states. In contrast to the closed curve of the Fermi
is similar to the case of CrxTiyS2.279 Furthermore, chalcogen surfaces of the surface states in topological insulators, the
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Figure 33. Band structure of 1Td-WTe2 with (b,c) and without SOC (a). The Weyl points are located approximately 50 meV above the Fermi
level. The distance between two Weyl points is approximately 0.7% of the BZ width. Reprinted with permission from ref 289. Copyright 2015
Macmillan Publishers Ltd.

Figure 34. (a,d,g,h) Theoretical and (b,c,d,f) experimental band structure of 1Td-MoTe2. A good agreement between the theoretical and
experimental results is observed. Reprinted with permission from ref 118. Copyright 2016 Macmillan Publishers Ltd.

Fermi surfaces of the Weyl semimetals are arc type, which Although the Weyl points exist, it should be located at or
connects a pair of two Weyl points.286,288 There are two types very near Fermi level and there should be no other state from
of Weyl semimetal, based on the shape of the Weyl cone. Type other bands contributing to density of states at the Fermi
I is representative for the Fermi surface shrinking to Weyl surface,170 unless the physical properties of Weyl points are
points. In contrast, type II of Weyl semimetals has tilting Weyl difficult to distinguish and be measured. Although a narrow
cones, giving rise to a Fermi surface consisting of both electron band gap semiconductor without inversion symmetry is
and hole carriers, as shown in Figure 32c,d.11,12,118,289 Type II proposed as a good material to explore Weyl semimetals,
Weyl semimetals can be viewed as inverted band structures of there is no clear guideline for searching materials satisfying all
indirect semiconductors (Figure 8d).
above conditions.170
The searching guidelines for materials revealing Weyl
The existence of Weyl cones and Fermi arcs have been
semimetals are still unknown. However, there is a high
possibility that the Weyl semimetal may exist in materials with proved from two different classes of material: type I, TaAs
no inversion or broken time reversal symmetry (e.g., magnetic family (e.g TaAs, TaP, NbAs, NbP) and type II, layered
materials).170,171 This condition is derived from the theoretical transition dichalcogennides, MoTe2.167 The WTe2, a sister
model based on the two-band system. In such conditions, the material of MoTe2, is predicted to be type II Weyl semimetal,
band is nondegenerate and the conditions for maintaining the but the detection of the Weyl characteristics is more
Weyl cone can be satisfied more easily. This means that not all challenging due to the short distance between the two Weyl
noninversion symmetry or magnetic materials will always have points.167,290−293 In this section, we focus on the band
the Weyl cone. There is another important condition. structure of 1Td WTe2 and MoTe2.
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Figure 35. (a−d, i−l) Topological Fermi arcs in MoTe2 from simulation and (e−h) ARPES measurements at different energy levels. Reprinted
with permission from ref 118. Copyright 2016 Macmillan Publishers Ltd.

Figure 33 shows the band structure of 1Td-WTe2 with (b,c) and hole pocket, respectively, as also observed in the ARPES
and without SOC (a) from the Σ to Γ points.289 The SOC is results (Figure 34e,f). It is noticed that the Weyl points of
very strong in WTe2, indicated by a notable difference in the MoTe2 are located at 5 and 45 meV above the Fermi level
band structure with and without SOC. The small gap of cutting from theoretical calculation as shown in Figure 34g.
points is fully opened when the SOC is included. Interestingly, One important feature of evidence for the Weyl semimetal is
the Weyl points appear in the kz = 0 plane along the K−K′ the existence of the Fermi arc (e.g., the topological surface
direction, as shown in Figure 33c. However, these points are state). While the arc can be clearly revealed in theoretical
approximately 0.052 and 0.058 eV above the Fermi energy. calculation, it is not easy to prove in experiments. In the case of
Furthermore, the distance between the two Weyls point is too MoTe2, the surface states are squeezed between the electron
small (about 0.7% of the BZ width), leading to difficulties in and hole pockets, which is difficult to be detected. An indirect
the detection of these points due to the limitation of resolution way is to use theoretical calculation as a guideline to see how
in the ARPES measurements.292,293 To overcome this issue, much consistency between the theoretical and experimental
the searching direction is being shifted toward MoTe2 and results, even with the iso-energetic surface. The evolution of
(W1−xMox)Te2 alloy.11,12,118,294,295 the surface state at different energies is measured, as shown in
Figure 34 shows the theoretical and experimental band Figure 35. Far from and below the Fermi level, the distance
structures of MoTe2.118 The calculated band structure between the topological (red indicator) and trivial (gray
including the surface state is shown in Figure 34a. The bulk indicator) surface state is increased and this is revealed in both
band structure is represented by the continuous spectrum due the theoretical calculations and experimental results, indicating
to the strong dispersion along the kz axis, while a sharp line the topological arc state of the Weyl semimetal characteristic of
indicates the surface state. The experimental ARPES is clearly MoTe2. An interesting property of the Weyl semimetal is the
large unsaturated magnetoresistance. Both classes of Weyl
consistent with the calculated band structure, except that the
semimetals reveal this characteristic.8,31,115,296,297 This origi-
band is p-doped with the Fermi level is shifted down by 20
nates from the coexistence of the electron and hole carriers,
meV. To make clarification between the bulk and surface
which is believed to be the main factor leading to the large
states, the band structures in Figures 34b,c is measured by p- magnetoresistance, similar to the case of the Bi crystal.166
and s-polarized light, respectively. The surface state (marked as
a black curve) and the bulk electron pocket (marked as blue)
are clearly observed using the p-polarized light. The spectral 7. SUMMARY AND PERSPECTIVES
function at the Fermi surface (e.g., the density of states at the 2D materials have been synthesized in a form of bulk via flux
Fermi surface) reveals a bell and bowtie shape for the electron method or CVT approaches, while monolayer or few-layer 2D
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materials have been synthesized via typical CVDs. Unlike the superconductivity. Furthermore, the native of the atomic
semiconducting components, mono- or few-layer metallic films thickness can take more advantages. One typical example is the
are still in the infancy stage. They can be easily oxidized under proximity effect, wherein the interaction between the 2D
ambient conditions or during synthesis, as already practiced in materials with the substrate will strongly affect to their
the monolayer 1T′-MoTe2,, making it difficult to generalize properties. Whether this coupling effect can enhance or
CVD approaches practiced during synthesis of semiconducting destroy the magnetism and superconductivity of the atomic
films. A special care is required to avoid such oxidation effects. thin layer is still unknown.
Use of comprehensive air-free vacuum system combining
various equipment such as material synthesis, characterization, AUTHOR INFORMATION
device fabrication, and measurements is perhaps necessary. Corresponding Author
Phase engineering is also a big issue which has several
challenges. A representative approach for transforming from *E-mail: [email protected].
semiconducting to metallic phase is chemical Li intercalation. ORCID
Yet, this phase is not stable and evolves eventually to Dinh Loc Duong: 0000-0002-4118-9589
semiconducting phase. Another approach is the phase
Young Hee Lee: 0000-0001-7403-8157
modulation of the atomic structure by physical approaches
such as temperature, light irradiation, strain, and carrier Author Contributions
∥
injection. One may also take a route to atomic alloying Gang Hee Han and Dinh Loc Duong contributed equally to
process to overcome such problematic issues. For example, this work.
WS2 and WSe2 are typically known as H-phase materials, Notes
whereas the WTe2 is Td phase which is monoclinic structure.
Tuning of the chalcogens contents in synthesis process The authors declare no competing financial interest.
(WS1−xTex or WSe1−xTex) will modulate electronic structures. Biographies
The work should be further verified with some theoretical and
experimental works. Gang Hee Han received his Ph.D. from the Department of Physics in
Challenges are in device applications, and one of the biggest Sungkyunkwan University in 2011 under the supervision of Prof.
issues is the achievement of ohmic contact. The phase Young Hee Lee. He joined the Department of Astronomy and Physics
transformation of semiconducting to metallic phase seems to in the University of Pennsylvania (UPenn) in the United States as a
be a shortcut to lower the contact resistance. Whether this postdoctoral position between 2012 and 2014. He is now a research
approach is universal or not is still not clear because this professor of IBS Center for Integrated Nanostructure Physics
strongly depends on the material. The use of h-BN layers (CINAP) from 2014 in Sungkyunkwan University (SKKU). His
between oxide layer and 2D layer or between metal electrode research has focused on the synthesis of low dimensional materials
and 2D can reduce the Schottky barrier height but whether this such as carbon nanotubes, graphene, hexagonal boron nitrides, and
achieves ohmic contact or not is still unknown. Using graphene layered transition metal dichalcogenides.
as an intermediate contact material is a promising method to Dinh Loc Duong received his Ph.D. from the Sungkyunkwan Institute
reduce the contact resistance, as previously reported.298−300 of Nanoscience and Nanotechnology (SAINT) in 2012 under the
Because the interaction between 2D materials and electrode supervision Prof. Young Hee Lee. After his first postdoc in the same
metal is quite weak, functionalization of the 2D materials on lab from 2012 to 2014, he joined the Max-Planck-Institute for Solid
the contact area prior to electrode metal deposition is also a State research in Kern’s department from 2014 to 2016 as a junior
possible approach to improve the contact resistance. scientist. He is now research professor at the IBS Center for
Graphene is a good candidate for future transparent Integrated Nanostructure Physics (CINAP), Sungkyunkwan Univer-
electrode. While the conductivity of m-LTMdCs may not sity (SKKU). His current research interests are 2D materials,
match with that of graphene, some 2D m-LTMdCs has strong including their growth, characterization, and applications.
anisotropy which reveals orientation-dependent optical and Dong Hoon Keum entered Uiduk University in 2007 as an
electrical properties. Frequency dependent conductivity in undergraduate. He received his B.S. degree from Yeungnam
particular at low frequency limit is interesting for RF devices. University. In 2011, he joined the Department of Energy Science,
While 1Td WTe2 and MoTe2 are proved to be the Weyl Sungkyunkwan University, as a Ph.D. candidate. His current research
semimetal, the Weyl points are located above the Fermi interests focus on the synthesis of two-dimensional materials and their
energy. This prevents to directly characterize the properties of applications.
the Weyl points by the electrical transport measurements.
Therefore, a good strategy of doping should be developed to Seok Joon Yun entered Sungkyunkwan University in 2006 as an
move the Fermi energy reach to the Weyl points. This work undergraduate and graduated in 2012. In 2012, he got into the
should involve both first-principle calculations and exper- Department of Energy Science, Sungkyunkwan University as a Ph.D.
imental measurements. Searching for rich classes of 2D candidate student under the supervision Prof. Young Hee Lee. He has
materials for Weyl semimetal is another open research area. been working on the synthesis of 2D materials such as graphene,
Many efforts have been spent for searching high temperature hexagonal-boron nitride, black phosphorus, and transition metal
superconductivity in the m-LTMdCs. Most m-LTMdCs follow dichalcogenides.
the BCS theory. This requires a high energy phonon, which is Prof. Young Hee Lee has been a full professor of the Physics
strongly coupled with electrons to form electron pairs. Department at SKKU, since 2001. He received his Ph.D. from Kent
However, the formation of the PLD phase indicates the State University in Ohio (1986) in Physics. Prior to joining SKKU in
softened phonons that have phonons with a quite low energy. 2001, Prof. Lee was a full professor in the Physics Department at
It gives rise to low Tc. Nevertheless, the m-LTMdCs are still a Chonbuk National University since 1986. He was a visiting scholar at
platform for verifying the validation of the theory applied for Ames Laboratory, Iowa State University, in 1989, IBM, Zurich, in

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1993, and Michigan State University in 1996. Currently, he is the Synthesis of Borophenes: Anisotropic, Two-Dimensional Boron
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Award, IMR, Chinese Academy of Sciences, China, in 2007, and
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Presidential Award in Science and Education in 2008, Eistein Award
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fundamental properties of nanostructures in 0D, 1D, 2D, and their (8) Keum, D. H.; Cho, S.; Kim, J. H.; Choe, D.-H.; Sung, H.-J.; Kan,
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