Single-layer Transition Metal Dichalcogenides Research Articles

Optical and Excitonic Properties of Atomically Thin Transition-Metal Dichalcogenides

Starting with the isolation of a single sheet of graphene, the study of layered materials has been one of the most active areas of condensed matter physics, chemistry, and materials science. Single-layer transition-metal dichalcogenides are direct-gap semiconducting analogs of graphene that exhibit novel electronic and optical properties. These features provide exciting opportunities for the discovery of both new fundamental physical phenomena as well as innovative device platforms. Here, we review the progress associated with the creation and use of a simple microscopic framework for describing the optical and excitonic behavior of few-layer transition-metal dichalcogenides, which is based on symmetry, band structure, and the effective interactions between charge carriers in these materials. This approach provides an often quantitative account of experiments that probe the physics associated with strong electron–hole interactions in these quasi two-dimensional systems and has been successfully employed by many groups to both describe and predict emergent excitonic behavior in these layered semiconducting systems.

CMOS-Compatible WS2-Based All-Optical Modulator

Two-dimensional materials are compatible with silicon complementary metal-oxide semiconductor processes. As such, the integration of two-dimensional materials with silicon-based semiconductors could lead to an amalgamation of the beneficial properties of both silicon and the two-dimensional material thereby facilitating improved performance. Single-layer transition metal dichalcogenide materials like MoS2, MoTe2 and WS2 are characterized by direct band gaps and possess high emission efficiencies. These materials are, therefore, perfectly suited for ameliorating the optical emission inadequacies of silicon-based-materials. In this study, we integrate WS2 with a silicon-based silicon-nitride waveguide to modulate a 532-nm pump light source, and successfully modulate and amplify an optical signal at 640 nm. Compared to other modulators based on two-dimensional materials, e.g., graphene, the proposed WS2-based modulator theoretically incurs lower losses and exhibits higher contrast levels and signal-to-noise ...

Novel doping alternatives for single-layer transition metal dichalcogenides

Successful doping of single-layer transition metal dichalcogenides (TMDs) remains a formidable barrier to their incorporation into a range of technologies. We use density functional theory to study doping of molybdenum and tungsten dichalcogenides with a large fraction of the periodic table. An automated analysis of the energetics, atomic and electronic structure of thousands of calculations results in insightful trends across the periodic table and points out promising dopants to be pursued experimentally. Beyond previously studied cases, our predictions suggest promising substitutional dopants that result in p-type transport and reveal interesting physics behind the substitution of the metal site. Doping with early transition metals (TMs) leads to tensile strain and a significant reduction in the bandgap. The bandgap increases and strain is reduced as the d-states are filled into the mid TMs; these trends reverse as we move into the late TMs. Additionally, the Fermi energy increases monotonously as the d-shell is filled from the early to mid TMs and we observe few to no gap states, indicating the possibility of both p- (early TMs) and n- (mid TMs) type doping. Quite surprisingly, the simulations indicate the possibility of interstitial doping of TMDs; the energetics reveal that a significant number of dopants, increasing in number from molybdenum disulfide to diselenide and to ditelluride, favor the interstitial sites over adsorbed ones. Furthermore, calculations of the activation energy associated with capturing the dopants into the interstitial site indicate that the process is kinetically possible. This suggests that interstitial impurities in TMDs are more common than thought to date and we propose a series of potential interstitial dopants for TMDs relevant for application in nanoelectronics based on a detailed analysis of the predicted electronic structures.

Universal spin dynamics in quantum wires

We discuss the universal spin dynamics in quasi one-dimensional systems including the real spin in narrow-gap semiconductors like InAs and InSb, the valley pseudospin in staggered single-layer graphene, and the combination of real spin and valley pseudospin characterizing single-layer transition metal dichalcogenides (TMDCs) such as MoS$_2$, WS$_2$, MoSe$_2$, and WSe$_2$. All these systems can be described by the same Dirac-like Hamiltonian. Spin-dependent observable effects in one of these systems thus have counterparts in each of the other systems. Effects discussed in more detail include equilibrium spin currents, current-induced spin polarization (Edelstein effect), and spin currents generated via adiabatic spin pumping. Our work also suggests that a long-debated spin-dependent correction to the position operator in single-band models should be absent.

Observation of topological states residing at step edges of WTe2

Topological states emerge at the boundary of solids as a consequence of the nontrivial topology of the bulk. Recently, theory predicts a topological edge state on single layer transition metal dichalcogenides with 1T’ structure. However, its existence still lacks experimental proof. Here, we report the direct observations of the topological states at the step edge of WTe2 by spectroscopic-imaging scanning tunneling microscopy. A one-dimensional electronic state residing at the step edge of WTe2 is observed, which exhibits remarkable robustness against edge imperfections. First principles calculations rigorously verify the edge state has a topological origin, and its topological nature is unaffected by the presence of the substrate. Our study supports the existence of topological edge states in 1T’-WTe2, which may envision in-depth study of its topological physics and device applications.

Low-temperature thermal transport and thermopower of monolayer transition metal dichalcogenide semiconductors

We study the low temperature thermal conductivity of single-layer transition metal dichalcogenides (TMDCs). In the low temperature regime where heat is carried primarily through transport of electrons, thermal conductivity is linked to electrical conductivity through the Wiedemann–Franz law (WFL). Using a k.p Hamiltonian that describes the and valley edges, we compute the zero-frequency electric (Drude) conductivity using the Kubo formula to obtain a numerical estimate for the thermal conductivity. The impurity scattering determined transit time of electrons which enters the Drude expression is evaluated within the self-consistent Born approximation. The analytic expressions derived show that low temperature thermal conductivity (1) is determined by the band gap at the valley edges in monolayer TMDCs and (2) in presence of disorder which can give rise to the variable range hopping regime, there is a distinct reduction. Additionally, we compute the Mott thermopower and demonstrate that under a high frequency light beam, a valley-resolved thermopower can be obtained. A closing summary reviews the implications of results followed by a brief discussion on applicability of the WFL and its breakdown in context of the presented calculations.

Interactions between copper and transition metal dichalcogenides: A density functional theory study

We characterized the interface between fcc Cu and various single-layer transition metal dichalcogenides (TMDs) using density functional theory calculations. We found that monolayer Mo, W, Nb, Ti, and V disulfides, diselenides, and ditellurides are stable on Cu(111) with binding energies higher than those of $h$-BN and graphene. An analysis of the electronic structure of the interfaces indicates partial covalent bonding and a complex redistribution of electronic density, consisting of electron accumulation in the gap region, depletion near the Cu and TMD surfaces, and charge density oscillations within both materials. The resulting net electric dipoles significantly alter the electron work function of the Cu surface. Interestingly, capping Cu(111) surfaces with group-IV and -V TMDs leads to an increase in the work function of up to 1 eV, while group-VI TMDs can decrease the work function by up to 1 eV. Finally, the complex charge distributions at the Cu/TMD interfaces include opposing dipoles and explain the fact that net dipoles associated with Cu/TMD interfaces are comparable to or smaller than those of Cu/graphene and Cu/$h$-BN, even though the Cu/TMD binding energies are significantly higher.

Exciton Dynamics, Transport, and Annihilation in Atomically Thin Two-Dimensional Semiconductors.

Large binding energy and unique exciton fine structure make the transition metal dichalcogenides (TMDCs) an ideal platform to study exciton behaviors in two-dimensional (2D) systems. While excitons in these systems have been extensively researched, there currently lacks a consensus on mechanisms that control dynamics. In this Perspective, we discuss extrinsic and intrinsic factors in exciton dynamics, transport, and annihilation in 2D TMDCs. Intrinsically, dark and bright exciton energy splitting is likely to play a key role in modulating the dynamics. Extrinsically, defect scattering is prevalent in single-layer TMDCs, which leads to rapid picosecond decay and limits exciton transport. The exciton-exciton annihilation process in single-layer TMDCs is highly efficient, playing an important role in the nonradiative recombination rate in the high exciton density regime. Future challenges and opportunities to control exciton dynamics are discussed.

Direct visualization of a two-dimensional topological insulator in the single-layer1T′−WTe2

We grow nearly freestanding single-layer 1T'-WTe2 on graphitized 6H-SiC(0001) by using molecular beam epitaxy (MBE), and characterize its electronic structure with scanning tunneling microscopy / spectroscopy (STM/STS). We demonstrate the existence of topological edge states at the periphery of single-layer WTe2 islands. Surprisingly, we also find a band gap in the bulk and the semiconducting behaviors of the single-layer WTe2 at low temperature, which is likely resulted from an incommensurate charge density wave (CDW) transition. The realization of two-dimensional topological insulators (2D TIs) in single-layer transition metal dichalcogenide (TMD) thus provides a promising platform for further exploration of the 2D TIs' physics and related applications.

Electronic and optical properties of vacancy defects in single-layer transition metal dichalcogenides

A detailed first-principle study has been performed to evaluate the electronic and optical properties of single-layer (SL) transition metal dichalcogenides (TMDCs) (MX${}_2$; M= transition metal such as Mo, W and X= S, Se, Te), in the presence of vacancy defects (VDs). Defects usually play an important role in tailoring electronic, optical, and magnetic properties of semiconductors. We consider three types of VDs in SL TMDCs i) $X$-vacancy, $X_{2}$-vacancy, and iii) $M$-vacancy. We show that VDs lead to localized defect states (LDS) in the band structure, which in turn give rise to sharp transitions in in-plane and out-of-plane optical susceptibilities, $\chi_{\parallel}$ and $\chi_{\perp}$. The effects of spin orbit coupling (SOC) are also considered. We find that SOC splitting in LDS is directly related to the atomic number of the transition metal atoms. Apart from electronic and optical properties we also find magnetic signatures (local magnetic moment of $\sim\mu_{B}$) in MoSe$_{2}$ in the presence of Mo vacancy, which breaks the time reversal symmetry and therefore lifts the Kramers degeneracy. We show that a simple qualitative tight binding model (TBM), involving only the hopping between atoms surrounding the vacancy with an on-site SOC term, is sufficient to capture the essential features of LDS. In addition, the existence of the LDS can be understood from the solution of the 2D Dirac Hamiltonian by employing infinite mass boundary conditions. In order to provide a clear description of the optical absorption spectra, we use group theory to derive the optical selection rules between LDS for both $\chi_{\parallel}$ and $\chi_{\perp}$.

A kinetic Monte Carlo simulation method of van der Waals epitaxy for atomistic nucleation-growth processes of transition metal dichalcogenides

Controlled growth of crystalline solids is critical for device applications, and atomistic modeling methods have been developed for bulk crystalline solids. Kinetic Monte Carlo (KMC) simulation method provides detailed atomic scale processes during a solid growth over realistic time scales, but its application to the growth modeling of van der Waals (vdW) heterostructures has not yet been developed. Specifically, the growth of single-layered transition metal dichalcogenides (TMDs) is currently facing tremendous challenges, and a detailed understanding based on KMC simulations would provide critical guidance to enable controlled growth of vdW heterostructures. In this work, a KMC simulation method is developed for the growth modeling on the vdW epitaxy of TMDs. The KMC method has introduced full material parameters for TMDs in bottom-up synthesis: metal and chalcogen adsorption/desorption/diffusion on substrate and grown TMD surface, TMD stacking sequence, chalcogen/metal ratio, flake edge diffusion and vacancy diffusion. The KMC processes result in multiple kinetic behaviors associated with various growth behaviors observed in experiments. Different phenomena observed during vdW epitaxy process are analysed in terms of complex competitions among multiple kinetic processes. The KMC method is used in the investigation and prediction of growth mechanisms, which provide qualitative suggestions to guide experimental study.

First Principle Investigation on Thermoelectric Properties of Transition Metal Dichalcogenides: Beyond the Rigid Band Model

The thermoelectric properties (electrical conductivity, Seebeck coefficient, and power factor) of single layer transition metal dichalcogenides (MoS2, MoSe2, WS2, and WSe2) are investigated theoretically on the basis of ab initio quantum transport using the Landauer Buttiker formalism. The often used rigid band model is compared to realistic doping, namely substitution and adsorption, it is found that several important physical insights governing the transport are missing in this approximation. The rigid band model appears to clearly overestimate the thermoelectic efficiency, hampering its relevance for thermoelectric studies. Substitution doping by chloride or phosphorus leads to poor power factor due to drastic changes of the pristine band structure. In contrast, adsorption doping by alkalies (Li, Na, K, and Rb) favors larger power factor. Realistic treatment of the disorder induced by the dopants is also investigated and reveals that Cl doping leads to very short localization length of 3.5 nm while K c...

Identifying and Visualizing the Edge Terminations of Single-Layer MoSe2 Island Epitaxially Grown on Au(111)

Recently, single-layer transition-metal dichalcogenides have drawn significant attention due to their remarkable physical properties in the monolayer as well as at the edges. Here, we constructed high-quality, single-layer MoSe2 islands on the Au(111) surfaces in ultrahigh vacuum by molecular beam epitaxy. All of the islands have hexagonal or triangular shapes with two kinds of well-defined edges. Scanning tunneling spectroscopy (STS) curves show notable differences in positive sample bias for the two types of edges. Density functional theory calculations for several edge configurations of MoSe2 confirm that the STS differences are attributed to the coupling between the pz orbital of Se atoms and the dxz orbital of Mo atoms, and the two types of observed edge terminations are the bare Se edge and selenium-saturated Mo edge.

Spin and valley control of free carriers in single-layer WS2

The semiconducting single-layer transition metal dichalcogenides have been identified as ideal materials for accessing and manipulating spin- and valley-quantum numbers due to a set of favorable optical selection rules in these materials. Here, we apply time- and angle-resolved photoemission spectroscopy to directly probe optically excited free carriers in the electronic band structure of a high quality single layer of WS$_2$. We observe that the optically generated free hole density in a single valley can be increased by a factor of 2 using a circularly polarized optical excitation. Moreover, we find that by varying the photon energy of the excitation we can tune the free carrier density in a given spin-split state around the valence band maximum of the material. The control of the photon energy and polarization of the excitation thus permits us to selectively excite free electron-hole pairs with a given spin and within a single valley.

Magnetism and magnetocrystalline anisotropy in vacancy doped and (non)metal adsorbed single-layer PtSe2

The single-layer (1L) transition-metal dichalcogenides (TMDs) have attracted great attentions over the past years. However, most of previous work focus on the Mo(W) TMDs and the pristine 1L-TMDs are often diamagnetic. Recent experimental progress has sparked renewed interest in Pt(Pd) TMDs. Here, using first-principles calculations, we study the functionalization of the newly synthesized 1L-PtSe2 through adatom adsorption and vacancy defect creation. It is found the 1L-PtSe2 with Pt vacancy (VPt) has large magnetocrystalline anisotropy energy (30.4meV/VPt), which is comparable with that of IrCo dimer adsorbed graphene. Except for the magnetism induced by the magnetic Fe(Co) adatom, the metal-free magnetism is introduced by the B(F) adatom, and the 1L-PtSe2 shows stronger adsorption capability to nonmetal atoms (H, B, C, N, F) than that of the 1L-MoS2(1L-MoSe2). In contrast to the case of 1L-MoS2(1L-MoSe2), significant reconstructions of surfaces are found for the H, B, C and N adsorbed 1L-PtSe2. Moreover, the semiconducting behaviors and spintronic features are modified: Fe(N) adatom causes n(p)-type doping, F adsorbed 1L-PtSe2 becomes bipolar semiconductor.

A systematic investigation of thermal conductivities of transition metal dichalcogenides

Although the thermal conductivities of MoS2 and WS2 have been reported by some experimental and theoretical studies, the results are inconsistent. Here, thermal transport properties of twelve types of single layer transition metal dichalcogenides (TMDs) MX2 (M=Cr, Mo, W; X=O, S, Se, Te) are investigated systematically, by solving Boltzmann transport equation based on first-principle calculations. After accurate considering the size effect and boundary scattering, we find that our calculations can fit the experimental results very well. Moreover, diverse transport properties in TMDs are revealed, and an abnormal dependence of thermal conductivity on atomic mass is observed. In most MX2 structures, the thermal conductivities decrease with the increase of mass of atom M or X. However, the thermal conductivities of sulfides MS2 and selenides MSe2 increase as the M changes from Cr to Mo to W, which is contradictory to our traditional understanding. A detailed calculation indicates that the abnormal trend is originated from the rapid increase of phonon relaxation time. Our studies provide important information for thermal transport abilities in TMDs.

Very high thermoelectric figure of merit found in hybrid transition-metal-dichalcogenides

The search for thermoelectrics with higher figures of merit (ZT) will never stop due to the demand of heat harvesting. Single layer transition metal dichalcogenides (TMD), namely, MX2 (where M is a transition metal and X is a chalcogen), that have electronic band gaps are among the new materials that have been the focus of such research. Here, we investigate the thermoelectric transport properties of hybrid armchair-edged TMD nanoribbons, by using the nonequilibrium Green's function technique combined with the first principles and molecular dynamics methods. We find a ZT as high as 7.4 in hybrid MoS2/MoSe2 nanoribbons at 800 K, creating a new record for ZT. Moreover, the hybrid interfaces by substituting X atoms are more efficient than those by substituting M atoms to tune the ZT. The origin of such a high ZT of hybrid nanoribbons is the high density of the grain boundaries: the hybrid interfaces decrease thermal conductance drastically without a large penalty to electronic conductance.

Magnetism and magnetocrystalline anisotropy in single-layer PtSe2: Interplay between strain and vacancy

The electronic and magnetic properties of the newly synthesized single-layer (1 L) transition-metal dichalcogenide (TMD) PtSe2 are studied by first-principles calculations. We find the strain or selenium vacancy (VSe) alone cannot induce the magnetism. However, an interplay between strain and VSe leads to the magnetism due to the breaking of Pt-Pt metallic bonds. Different from the case of 1 L-MoS2 with VS, the defective 1 L-PtSe2 has the spatially extended spin density, which is responsible for the obtained long range ferromagnetic coupling. Moreover, the 1 L-PtSe2 with VSe undergoes a spin reorientation transition from out-of-plane to in-plane magnetization, accompanying a maximum magnetocrystalline anisotropy energy of ∼9–10.6 meV/VSe. These results indicate the strain not only can effectively tune the magnetism but also can manipulate the magnetization direction of 1 L-TMDs.

Photoinduced charge transfer from vacuum-deposited molecules to single-layer transition metal dichalcogenides

Variations of photoluminescence (PL) and Raman spectra of single-layer MoS2, MoSe2, WS2, and WSe2 due to the vacuum deposition of C60 or copper phthalocyanine (CuPc) molecules have been investigated. PL spectra are decomposed into two competitive components, an exciton and a charged exciton (trion), depending on carrier density. The variation of PL spectra is interpreted in terms of charge transfer across the interfaces between transition metal dichalcogenides (TMDs) and dopant molecules. We find that deposited C60 molecules inject photoexcited electrons into MoS2, MoSe2, and WS2 or holes into WSe2. CuPc molecules also inject electrons into MoS2, MoSe2, and WS2, while holes are depleted from WSe2 to CuPc. We then propose a band alignment between TMDs and dopant molecules. Peak shifts of Raman spectra and doped carrier density estimated using a three-level model also support the band alignment. We thus demonstrate photoinduced charge transfer from dopant molecules to single-layer TMDs.

Electron energy loss spectroscopy of excitons in two-dimensional-semiconductors as a function of temperature

We have explored the benefits of performing monochromated Electron Energy Loss Spectroscopy (EELS) in samples at cryogenic temperatures. As an example, we have observed the excitonic absorption peaks in single layer Transition Metal Dichalcogenides. These peaks appear separated by small energies due to spin orbit coupling. We have been able to distinguish the split for MoS2 below 300 K and for MoSe2 below 220 K. However, the distinction between peaks is only clear at 150 K. We have measured the change in absorption threshold between 150 K and 770 K for MoS2 and MoSe2. We discuss the effect of carbon and ice contamination in EELS spectra. The increased spectral resolution available made possible with modern monochromators in electron microscopes will require the development of stable sample holders which reaches temperatures far below that of liquid nitrogen.