Single-layer metal dichalcogenides are two-dimensional semiconductors that present strong potential for electronic and sensing applications complementary to that of graphene.

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Electronics and optoelectronics of two-dimensional transition metal dichalcogenides.

Ultrathin two-dimensional nanosheets of layered transition metal dichalcogenides (TMDs) are fundamentally and technologically intriguing. In contrast to the graphene sheet, they are chemically versatile. Mono- or few-layered TMDs - obtained either through exfoliation of bulk materials or bottom-up syntheses - are direct-gap semiconductors whose bandgap energy, as well as carrier type (n- or p-type), varies between compounds depending on their composition, structure and dimensionality. In this Review, we describe how the tunable electronic structure of TMDs makes them attractive for a variety of applications. They have been investigated as chemically active electrocatalysts for hydrogen evolution and hydrosulfurization, as well as electrically active materials in opto-electronics. Their morphologies and properties are also useful for energy storage applications such as electrodes for Li-ion batteries and supercapacitors.

http://nanotubes.rutgers.edu/PDFs/nchem_TMDs_2013.pdf

The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets

Graphene is very popular because of its many fascinating properties, but its lack of an electronic bandgap has stimulated the search for 2D materials with semiconducting character. Transition metal dichalcogenides (TMDCs), which are semiconductors of the type MX2, where M is a transition metal atom (such as Mo or W) and X is a chalcogen atom (such as S, Se or Te), provide a promising alternative. Because of its robustness, MoS2 is the most studied material in this family. TMDCs exhibit a unique combination of atomic-scale thickness, direct bandgap, strong spin–orbit coupling and favourable electronic and mechanical properties, which make them interesting for fundamental studies and for applications in high-end electronics, spintronics, optoelectronics, energy harvesting, flexible electronics, DNA sequencing and personalized medicine. In this Review, the methods used to synthesize TMDCs are examined and their properties are discussed, with particular attention to their charge density wave, superconductive and topological phases. The use of TMCDs in nanoelectronic devices is also explored, along with strategies to improve charge carrier mobility, high frequency operation and the use of strain engineering to tailor their properties. Two-dimensional transition metal dichalcogenides (TMDCs) exhibit attractive electronic and mechanical properties. In this Review, the charge density wave, superconductive and topological phases of TMCDs are discussed, along with their synthesis and applications in devices with enhanced mobility and with the use of strain engineering to improve their properties.

2D transition metal dichalcogenides

Dimensionality plays a critical role in determining the properties of materials due to, for example, the different ways that electrons interact in three-dimensional, twodimensional (2D), and one-dimensional (1D) structures.1-5 The study of dimensionality has a long history in chemistry and physics, although this has been primarily with the prefix “quasi” added to the description of materials; that is, quasi-1D solids, including square-planar platinum chain and metal trichalcogenide compounds,2,6 and quasi2D layered solids, such as metal dichalcogenides and copper oxide superconductors.3-5,7,8 The anisotropy inherent in quasi-1D and -2D systems is central to the unique properties and phases that these materials exhibit, although the small but finite interactions between 1D chains or 2D layers in bulk materials have made it difficult to address the interesting properties expected for the pure low-dimensional systems. Are pure low-dimensional systems interesting and worth pursuing? We believe that the answer to this question is an unqualified yes from the standpoints of both fundamental science and technology. One needs to look no further than past studies of the 2D electron gas in semiconductor heterostructures, which have produced remarkably rich and often unexpected results,9,10 and electron tunneling through 0D quantum dots, which have led to the concepts of the artificial atom and the creation of single electron transistors.11-15 In these cases, lowdimensional systems were realized by creating discrete 2D and 0D nanostructures. 1D nanostructures, such as nanowires and nanotubes, are expected to be at least as interesting and important as 2D and 0D systems.16,17 1D systems are the smallest dimension structures that can be used for efficient transport of electrons and optical excitations, and are thus expected to be critical to the function and integration of nanoscale devices. However, little is known about the nature of, for example, localization that could preclude transport through 1D systems. In addition, 1D systems should exhibit density of states singularities, can have energetically discrete molecularlike states extending over large linear distances, and may show more exotic phenomena, such as the spin-charge separation predicted for a Luttinger liquid.1,2 There are also many applications where 1D nanostructures could be exploited, including nanoelectronics, superstrong and tough composites, functional nanostructured materials, and novel probe microscopy tips.16-29 To address these fascinating fundamental scientific issues and potential applications requires answers to two questions at the heart of condensed matter chemistry and physics research: (1) How can atoms or other building blocks be rationally assembled into structures with nanometer-sized diameters but much longer lengths? (2) What are the intrinsic properties of these quantum wires and how do these properties depend, for example, on diameter and structure? Below we describe investigations from our laboratory directed toward these two general questions. The organization of this Account is as follows. In section II, we discuss the development of a general approach to the rational synthesis of crystalline nanowires of arbitrary composition. In section III, we outline key challenges to probing the intrinsic properties of 1D systems and illustrate solutions to these challenges with measurements of the atomic structure and electronic properties of carbon nanotubes. Last, we discuss future directions and challenges in section IV.

http://cmliris.harvard.edu/assets/AccChemRes_32_435.pdf

Chemistry and Physics in One Dimension: Synthesis and Properties of Nanowires and Nanotubes

In recent years, we have seen a rapid progress in the field of graphene plasmonics, motivated by graphene's unique electrical and optical properties, tunabilty, long-lived collective excitation and their extreme light confinement. Here, we review the basic properties of graphene plasmons; their energy dispersion, localization and propagation, plasmon-phonon hybridization, lifetimes and damping pathways. The application space of graphene plasmonics lies in the technologically significant, but relatively unexploited terahertz to mid-infrared regime. We discuss emerging and potential applications, such as modulators, notch filters, polarizers, mid-infrared photodetectors, mid-infrared vibrational spectroscopy, among many others.

Graphene Plasmonics for Terahertz to Mid-Infrared Applications

The d1 layer metals TaS2, TaSe2, NbSe2, in all their various polytypic modifications, acquire, below some appropriate temperature, phase conditions that their electromagnetic properties have previously revealed as ‘anomalous’. Our present electron-microscope studies indicate that this anomalous behaviour usually includes the adoption, at some stage, of a superlattice. The size of superlattice adopted often is forecast in the pattern of satellite spotting and strong diffuse scattering found above the transition. Our conclusions are that charge-density waves and their concomitant periodic structural distortions occur in all these 4d1/5d1 dichalcogenides. We have related the observed periodicities of these CDW states to the theoretical form of the parent Fermi surfaces. Particularly for the 1T octahedrally coordinated polytypes the Fermi surface is very simple and markedly two-dimensional in character, with large near-parallel walls. Such a situation is known theoretically to favour the formation of...

Charge-density waves and superlattices in the metallic layered transition metal dichalcogenides

Effects of doping on charge-density waves in layer compounds

Through detailed examination of the crystal structure and bonding conditions in the trichalcogenides, it has been possible to gain a deeper understanding of the band structure of these complex materials, and with this of their unusual electronic behavior. The character of the observed semimetallicity in Ta${\mathrm{Se}}_{3}$ and Nb${\mathrm{Se}}_{3}$ is much clarified. Each material in the group-V family is seen to achieve a very individually tailored band structure, enfolding the various structural and energy-level adjustments. The nonuniformity and the molecularization of these structures contrasts strongly with the dichalcogenide behavior. The structural, if not the electronic, dimensionality of the group-V trichalcogenides remains closer to two than to one. It is found that the periodic structural distortions developed by Nb${\mathrm{Se}}_{3}$ are probably more suited to a metal-metal bonding description than to the traditional Fermi surface determined instability of a charge-density wave. The field-induced sliding of these distortions can then be described in terms of cooperative bond flipping through a discommensurate superlattice. We examine in crystal chemical terms why this motion is so unusually weakly pinned to defects and impurities in Nb${\mathrm{Se}}_{3}$. In fact, the investigation shows that it will be very hard to find a material better suited to the realization of this phenomenon.

Bands, bonds, and charge-density waves in the Nb Se 3 family of compounds

Concerning the semimetallic characters of TiS2 and TiSe2

An attempt has been made to understand the detailed form and phasing taken by the periodic-structural distortions (PSD) as developed in the various ${d}^{1}\ensuremath{-}{d}^{0}$ charge-density-wave (CDW) bearing materials. The diagrammatic mode of presentation which is used facilitates insight into the forces at work at the unit-cell level. In the fully investigated case of the $2H$ structure, with its trigonal prismatically coordinated sandwiches, these are able to modify substantially the simple relationship between PSD and CDW. The proposed phasing of the CDW in the case of $1T\ensuremath{-}\mathrm{T}\mathrm{a}{\mathrm{S}}_{2}$ ($1T\ensuremath{-}\mathrm{T}\mathrm{a}{\mathrm{Se}}_{2}$) goes against recent interpretation of the available data, and a revised interpretation of that data is given. The two PSD's reported for Nb${\mathrm{Te}}_{2}$ have for the first time been brought satisfactorily into the present CDW scheme. $3{d}^{1}$ V${\mathrm{Se}}_{2}$ and $3{d}^{0}$ Ti${\mathrm{Se}}_{2}$ provide interesting and illuminating contrasts in behavior compared with $5{d}^{1}$ $1T\ensuremath{-}\mathrm{T}\mathrm{a}{\mathrm{Se}}_{2}$.

Questions concerning the form taken by the charge-density wave and the accompanying periodic-structural distortions in 2 H − T a Se 2 , and closely related materials

J. A. Wilson

Papers

Charge-density waves and superlattices in the metallic layered transition metal dichalcogenides

Effects of doping on charge-density waves in layer compounds

Bands, bonds, and charge-density waves in the Nb Se 3 family of compounds

Concerning the semimetallic characters of TiS2 and TiSe2

Questions concerning the form taken by the charge-density wave and the accompanying periodic-structural distortions in 2 H − T a Se 2 , and closely related materials