Joint density of states and charge density wave in 2H-structured transition metal dichalcogenides

The joint density of states of two different 2H-structured transition metal dichalcogenides (TMDs) with and without charge density wave (CDW), Na_0.05TaS₂ and Cu_0.09NbS₂, respectively, are compared. While there is a clear maximum at the 3×3 charge density wavevector for Na_0.05TaS₂, the joint density of states for Cu_0.09NbS₂ does not show such behavior, consistent with the absence of CDW in the system. Our results illustrate that the joint density of states well represents the charge instability in 2D systems.     

Topological superconductivity in Janus monolayer transition metal dichalcogenides

The Janus monolayer transition metal dichalcogenides (TMDs) $MXY$ ($M={\rm Mo}$, W, $etc$. and $X, Y={\rm S}$, Se, $etc$.) have been successfully synthesized in recent years. The Rashba spin splitting in these compounds arises due to the breaking of out-of-plane mirror symmetry. Here we study the pairing symmetry of superconducting Janus monolayer TMDs within the weak-coupling framework near critical temperature $T_{\rm c}$, of which the Fermi surface (FS) sheets centered around both $ărGamma$ and $K (K')$ points. We find that the strong Rashba splitting produces two kinds of topological superconducting states which differ from that in its parent compounds. More specifically, at relatively high chemical potentials, we obtain a time-reversal invariant $s + f + p$-wave mixed superconducting state, which is fully gapped and topologically nontrivial, $i.e.$, a $\mathbb{Z}_2$ topological state. On the other hand, a time-reversal symmetry breaking $d + p + f$-wave superconducting state appears at lower chemical potentials. This state possess a large Chern number $|C|=6$ at appropriate pairing strength, demonstrating its nontrivial band topology. Our results suggest the Janus monolayer TMDs to be a promising candidate for the intrinsic helical and chiral topological superconductors.     

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

The d1 layer metals TaS 2 , TaSe 2 , NbSe 2 , 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-microscopic studies indicate that this anomalous behaviour usually included 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 4d 1 /5d 1 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 and spin-density waves. When they first appear, the CDWs in the 1T (and 4Hb) polytypes are incommensurate with the lattice. This condition produes a fair amount of gapping in the density of states at the Fermi level. For the simplest case of 1T-TaSe 2 , the room temperature superlattice is realized when this existing CDW rotates into an orientation for which it then become commensurate. At this first-order transition the Fermi surface energy gapping increases beyond that generated by the incommensurate CDW, as is clearly evident in the electromagnetic properties. For the trigonal prismatically coordinated polytypes, CDW formation is withheld to low temperatures, probably because of the more complex band structures. This CDW state (in the cases measured) would seem at once commensurate, even though the transition is, from a wide variety of experiments, apparently second order. A wide range of doped and intercalated materials have been used to substantiate the presence of CDWs in these compounds, and to clarify the effect that their occurrence has on the physical properties. The observations further demonstrate the distinctiveness of the transition metal dichalcogenide layer compounds, and of the group VA metals in particular.     

Recent developments in CVD growth and applications of 2D transition metal dichalcogenides

Two-dimensional (2D) transition metal dichalcogenides (TMDs) with fascinating electronic energy band structures, rich valley physical properties and strong spin–orbit coupling have attracted tremendous interest, and show great potential in electronic, optoelectronic, spintronic and valleytronic fields. Stacking 2D TMDs have provided unprecedented opportunities for constructing artificial functional structures. Due to the low cost, high yield and industrial compatibility, chemical vapor deposition (CVD) is regarded as one of the most promising growth strategies to obtain high-quality and large-area 2D TMDs and heterostructures. Here, state-of-the-art strategies for preparing TMDs details of growth control and related heterostructures construction via CVD method are reviewed and discussed, including wafer-scale synthesis, phase transition, doping, alloy and stacking engineering. Meanwhile, recent progress on the application of multi-functional devices is highlighted based on 2D TMDs. Finally, challenges and prospects are proposed for the practical device applications of 2D TMDs.     

Coexistence of gapless excitations and commensurate charge-density wave in the 2H transition metal dichalcogenides

An unexpected feature common to 2H transition metal dichalcogenides ( 2H TMDs) is revealed with a first-principles Wannier function analysis of the electronic structure of the prototype 2H TaSe2: The low-energy Ta "5d(z2)" bands governing the physics of a charge-density wave (CDW) is dominated by hopping between next-nearest neighbors. With this motivation we develop a minimal effective model for the CDW formation, in which the unusual form of the hopping leads to an approximate decoupling of the three sublattices. In the CDW phase one sublattice remains undistorted, leaving the bands associated with it ungapped everywhere in the Fermi surface, resolving the long-standing puzzle of the coexistence of gapless excitations and commensurate CDW in the 2H TMDs.     

Charge order, metallic behavior, and superconductivity in La2-xBaxCuO4 with x=1/8

The ab-plane optical properties of a cleaved single crystal of La2-xBaxCuO4 for x=1/8 (Tc approximately =2.4 K) have been measured over a wide frequency and temperature range. The low-frequency conductivity is Drude-like and shows a metallic response with decreasing temperature. However, below approximately =60 K, corresponding to the onset of charge-stripe order, there is a rapid loss of spectral weight below about 40 meV. The behavior is quite different from that typically associated with the pseudogap in the normal state of the cuprates. Instead, the gapping of the normal-state single-particle excitations looks surprisingly similar to that observed in superconducting La2-xSrxCuO4, including the presence of a residual Drude peak with reduced weight.     

Defect repairing in two-dimensional transition metal dichalcogenides

Atomically thin two-dimensional (2D) transition metal dichalcogenides (TMDCs) have stimulated enormous research interest due to rich phase structure, high theoretical carrier mobility and layer-dependent bandgap. In view of the close correlation between defects and properties in 2D TMDCs, more attentions have been paid on the defect engineering in recent years, however the mechanism is still unclear. Herein, we review the critical progress of defect engineering and provide an extensive way to modulate the properties depressed by defects. To insight into the defect engineering, we firstly introduce two common kinds of defects during the growth progress of TMDCs and the possible distribution of energy levels those defects could induce. Then, various methods to improve point defects and grain boundaries during the period of growth are discussed intensively, with the assistance of which more large-area TMDCs films can be obtained. Considering the defects in TMDCs are inevitable regardless of concentration, we also highlight strategies to heal the defects after growth. Through dry methods or wet methods, the chalcogen vacancies can be repaired and thus, the performance of electronic device would be significantly enhanced. Finally, we propose the challenges and prospective for defect engineering in 2D TMDCs materials to support the optimization of device and lead them to wide applied fields.     

Strong correlations in two-dimensional transition metal dichalcogenides

Since the discovery of graphene, the development of two-dimensional material research has enabled the exploration of a rich variety of exotic quantum phenomena that are not accessible in bulk materials. These two-dimensional materials offer a unique platform to build novel quantum devices. Layered transition metal dichalcogenides, when thinned down to atomic thicknesses,exhibit intriguing physical properties such as strong electron correlations. The study of strongly-correlated phenomena in twod...     

Optical transitions in group V transition metal dichalcogenides

A comparison of the correspondent structures of thermoreflectance spectra in NbSe₂, TaSe₂, NbTe₂ gives indications in favour d-d transitions as responsible of the main features of the optical spectra at relatively low energies. Besides, a temperature broadened saddle point in the joint density of states in NbSe₂ is identified.     

Chemical bonding and structure in layered transition metal dichalcogenides

Recent infrared reflectivity measurements on the transition metal dichalcogenides show striking differences among these compounds. The consequences of these differences on their band structures is discussed.     

Phenomenology of antiferromagnetic metal-insulator transition in 3d transition metal dichalcogenides

A phenomenological theory is set up to describe the metal-insulator transition at T = 0 between phases which both exhibit cooperative antiferromagnetic ordering. A prediction which emerges relates the antiferromagnetic moment to Fermiology in the metal. Possible experiments on 3d transition metal dichalogenides are thereby suggested.     

Charge density wave transition in Na2Ti2Sb2O probed by 23Na NMR

Herein we investigated the electronic properties of layered transition-metal oxides Na2Ti2Sb2O by23Na nuclear magnetic resonance(NMR)measurement.The resistivity,susceptibility and specific heat measurements show a phase transition at approximately 114 K(TA).No splitting or broadening in the central line of23Na NMR spectra is observed below and above the transition temperature indicating no internal field being detected.The spin-lattice relaxation rate divided by T(1/T1T)shows a sharp drop at about 110 K which suggests a gap opening behavior.Below the phase transition temperature zone,1/T1T shows Fermi liquid behavior but with much smaller value indicating the loss of large part of electronic density of states(DOS)because of the gap.No signature of the enhancement of spin fluctuations or magnetic order is found with the decreasing temperature.These results suggest a commensurate charge-density-wave(CDW)phase transition occurring.     

Strain effects on phase transitions in transition metal dichalcogenides

We perform density functional theory calculation to investigate the structural and electronic properties of various two-dimensional transition metal dichalcogenides, MX₂ (M=Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, or W, and X=S or Se), and their strain-induced phase transitions. We evaluate the relative stability and the activation barrier between the octahedral-T and the trigonal-H phases of each MX₂. It is found that the equilibrium and phase transition characteristics of MX₂ can be classified by the group to which its metal element M belongs in the periodic table. MX₂ with M in the group 4 (Ti, Zr, or Hf), forms an octahedral-T phase, while that with an M in the group 6 (Cr, Mo, or W) does a trigonal-H phase. On the other hand, MX₂ with M in the group 5 (V, Nb, or Ta), which is in-between the groups 4 and 6, may form either phase with a similar stability. It is also found that their electronic structures are strongly correlated to the structural configurations: mostly metallic in the T phase, while semiconducting in the H phase, although there are some exceptions. We also explore the effects of an applied stress and find for some MX₂ materials that the resultant strain, either tensile or compressive, may induce a structural phase transition by reducing the transition energy barrier, which is, in some cases, accompanied by its metal-insulator transition.     

Synthesis and characterization of 2D transition metal dichalcogenides: Recent progress from a vacuum surface science perspective

Layered transition metal dichalcogenides (TMDs) are a diverse group of materials whose properties vary from semiconducting to metallic with a variety of many body phenomena, ranging from charge density wave (CDW), superconductivity, to Mott-insulators. Recent interest in topologically protected states revealed also that some TMDs host bulk Dirac- or Wyle-semimetallic states and their corresponding surface states. In this review, we focus on the synthesis of TMDs by vacuum processes, such as molecular beam epitaxy (MBE). After an introduction of these preparation methods and categorize the basic electronic properties of TMDs, we address the characterization of vacuum synthesized materials in their ultrathin limit-mainly as a single monolayer material. Scanning tunneling microscopy and angle resolved photoemission spectroscopy has revealed detailed information on how monolayers differ in their properties from multi-layer and bulk materials. The status of monolayer properties is given for the TMDs, where data are available. Distinct modifications of monolayer properties compared to their bulk counterparts are highlighted. This includes the well-known transition from indirect to direct band gap in semiconducting group VI-B TMDs as the material-thickness is reduced to a single molecular layer. In addition, we discuss the new or modified CDW states in monolayer VSe₂ and TiTe₂, a Mott-insulating state in monolayer 1T-TaSe₂, and the monolayer specific 2D topological insulator 1T′-WTe₂, which gives rise to a quantum spin Hall insulator. New structural phases, that do not exist in the bulk, may be synthesized in the monolayer by MBE. These phases have special properties, including the Mott insulator 1T-NbSe₂, the 2D topological insulators of 1T′-MoTe₂, and the CDW material 1T-VTe₂. After discussing the pure TMDs, we report the properties of nanostructured or modified TMDs. Edges and mirror twin grain boundaries (MTBs) in 2D materials are 1D structures. In group VI-B semiconductors, these 1D structures may be metallic and their properties obey Tomonaga Luttinger quantum liquid behavior. Formation of Mo-rich MTBs in Mo-dichalcogenides and self-intercalation in between TMD-layers are discussed as potential compositional variants that may occur during MBE synthesis of TMDs or may be induced intentionally during post-growth modifications. In addition to compositional modifications, phase switching and control, in particular between the 1H and 1T (or 1T′) phases, is a recurring theme in TMDs. Methods of phase control by tuning growth conditions or by post-growth modifications, e.g. by electron doping, are discussed. The properties of heterostructures of TMD monolayers are also introduced, with a focus on lateral electronic modifications in the moiré-structures of group VI-B TMDs. The lateral potential induced in the moiré structures forms the basis of the currently debated moiré-excitons. Finally, we review a few cases of molecular adsorption on nanostructured monolayer TMDs. This review is intended to present a comprehensive overview of vacuum studies of fundamental materials' properties of TMDs and should complement the investigations on TMDs prepared by exfoliation or chemical vapor deposition and their applications.     

Charge density wave and superconductivity in 2H- and 4H-NbSe<Subscript>2</Subscript>: A revisit

Good-quality hexagonal NbSe₂ single crystals were prepared. In 2H-NbSe₂, superconducting and charge density wave (CDW) transitions were found at T _s = 7.4 K and T _c = 35 K respectively as reported previously. We have noticed that these two transitions are changed to T _c = 42 K and T _s = 6.5 K, in 4H-NbSe₂. Thermopower has shown clear anomaly at CDW transitions. The anisotropic upper critical field was calculated as ~3 and 6.3 for 2H- and 4H-single crystals around t = 0.81, where t = T/T _s, from resistivity and explained in terms of coherence length. From the relation, H_c2 (T)=H_c2 (0)[1-t²]H_{\rm c2} (T)=H_{\rm c2} (0)[1-t^2], H_c2^l (0)H_{\rm c2}^l (0) was calculated as ~8.15 T and 16.98 T at t = 0.84 in 2H-NbSe₂ and 4H-NbSe₂ respectively. However, H_c2^t (0) = 2.68H_{\rm c2}^t (0) = 2.68T for both single crystals.     

Charge density wave transition and nonlinear conductivity in NbS3

We report dc conductivity (σ) measurements on the linear chain compound NbS₃. The temperature dependence of σ indicates a phase trànsition at T_MI = 155 K with strong one-dimensional fluctuations above T_MI. Below T_MI the conductivity is strongly increasing with increasing electric field above a threshold field E_T, and is also strongly frequency dependent. We argue that the nonlinear conductivity is due to sliding charge density waves.     

Unconventional superconductivity in low density electron systems and conventional superconductivity in hydrogen metallic alloys

In this short review, we first discuss the results, which are mainly devoted to the generalizations of the famous Kohn–Luttinger mechanism of superconductivity in purely repulsive fermion systems at low electron densities. In the context of repulsive-U Hubbard model and Shubin–Vonsovsky model we consider briefly the superconducting phase diagrams and the symmetries of the order parameter in novel strongly correlated electron systems including idealized monolayer and bilayer graphene. We stress that purely repulsive fermion systems are mainly the subject of unconventional low-temperature superconductivity. To get the high temperature superconductivity in cuprates (with T_C of the order of 100 K) we should proceed to the t–J model with the van der Waals interaction potential and the competition between short-range repulsion and long-range attraction. Finally we note that to describe superconductivity in metallic hydrogen alloys under pressure (with T_C of the order of 200 K) it is reasonable to reexamine more conventional mechanisms connected with electron–phonon interaction. These mechanisms arise in the attractive-U Hubbard model with static onsite or intersite attractive potential or in more realistic theories (which include retardation effects) such as Migdal–Eliashberg strong coupling theory or even Fermi–Bose mixture theory of Ranninger et al. and its generalizations.     

Charge density wave states in phase-engineered monolayer VTe2

Charge density wave (CDW) strongly affects the electronic properties of two-dimensional (2D) materials and can be tuned by phase engineering. Among 2D transitional metal dichalcogenides (TMDs), VTe$_{2}$ was predicted to require small energy for its phase transition and shows unexpected CDW states in its T-phase. However, the CDW state of H-VTe$_{2}$ has been barely reported. Here, we investigate the CDW states in monolayer (ML) H-VTe$_{2}$, induced by phase-engineering from T-phase VTe$_{2}$. The phase transition between T- and H-VTe$_{2}$ is revealed with x-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM) measurements. For H-VTe$_{2}$, scanning tunneling microscope (STM) and low-energy electron diffraction (LEED) results show a robust $2sqrt 3 times 2sqrt 3 $ CDW superlattice with a transition temperature above 450 K. Our findings provide a promising way for manipulating the CDWs in 2D materials and show great potential in its application of nanoelectronics.     

Electron energy loss studies in solids; The transition metal dichalcogenides

The theory of characteristic electron energy losses is discussed in terms of the electronic band structure of a solid. The relationship between the observed plasmon energies, the average interband energy gap and the background dielectric constant of the solid is developed.

The transmission energy loss spectra of a number of the layer-type transition metal dichalcogenides, MX₂, where M=Zr, Hf, Nb, Ta, Mo and W and X=S and Se, have been measured in the range of 0–50 eV. In the experiments, a beam of 50 keV electrons is incident along the c-axis of the crystals and electrons inelastically scattered through an angle of 1 m radian are selected for energy analysis. This ensures that the momentum transfer and hence the electric vector for the excitations lies in the basal plane of the crystal (E⊥c).

Kramers-Kronig analysis has been applied to the energy loss data to deduce the complex dielectric function of each material. From this function, all other ‘optical’ constants, such as the reflectivity, and the oscillator integral function and joint density of states function have been calculated.

The results give substantial support to the existing band model for the family of materials and, in addition, provide the basis for a quantitative understanding of the band structure of individual compounds.