Monolayers Of Semiconducting Transition Metal Dichalcogenides Research Articles

The deep-acceptor nature of the chalcogen vacancies in 2D transition-metal dichalcogenides

Chalcogen vacancies in the semiconducting monolayer transition-metal dichalcogenides (TMDs) have frequently been invoked to explain a wide range of phenomena, including both unintentional p-type and n-type conductivity, as well as sub-band gap defect levels measured via tunneling or optical spectroscopy. These conflicting interpretations of the deep versus shallow nature of the chalcogen vacancies are due in part to shortcomings in prior first-principles calculations of defects in the semiconducting two-dimensional TMDs that have been used to explain experimental observations. Here we report results of hybrid density functional calculations for the chalcogen vacancy in a series of monolayer TMDs, correctly referencing the thermodynamic charge transition levels to the fundamental band gap (as opposed to the optical band gap). We find that the chalcogen vacancies are deep acceptors and cannot lead to n-type or p-type conductivity. Both the (0/−1) and (−1/−2) transition levels occur in the gap, leading to paramagnetic charge states S=1/2 and S = 1, respectively, in a collinear-spin representation. We discuss trends in terms of the band alignments between the TMDs, which can serve as a guide to future experimental studies of vacancy behavior.

Kapitza-resistance-like exciton dynamics in atomically flat MoSe2-WSe2 lateral heterojunction

Being able to control the neutral excitonic flux is a mandatory step for the development of future room-temperature two-dimensional excitonic devices. Semiconducting Monolayer Transition Metal Dichalcogenides (TMD-ML) with extremely robust and mobile excitons are highly attractive in this regard. However, generating an efficient and controlled exciton transport over long distances is a very challenging task. Here we demonstrate that an atomically sharp TMD-ML lateral heterostructure (MoSe2-WSe2) transforms the isotropic exciton diffusion into a unidirectional excitonic flow through the junction. Using tip-enhanced photoluminescence spectroscopy (TEPL) and a modified exciton transfer model, we show a discontinuity of the exciton density distribution on each side of the interface. We introduce the concept of exciton Kapitza resistance, by analogy with the interfacial thermal resistance referred to as Kapitza resistance. By comparing different heterostructures with or without top hexagonal boron nitride (hBN) layer, we deduce that the transport properties can be controlled, over distances far greater than the junction width, by the exciton density through near-field engineering and/or laser power density. This work provides a new approach for controlling the neutral exciton flow, which is key toward the conception of excitonic devices.

Valley Polarized Holes Induced Exciton Polaron Valley Splitting.

Monolayer transition metal dichalcogenide semiconductors are promising valleytronic materials. Among various quasi-particle excitations hosted by the system, the valley polarized holes are particularly interesting due to their long valley lifetime preserved by the large spin-orbit splitting and spin-valley locking in the valence band. Here we report that in the absence of any magnetic field a surprising valley splitting of exciton polarons can be induced by such valley polarized holes in monolayer WSe2. The size of the splitting is comparable to that of the Zeeman effect in a magnetic field as high as 7 T and offers a quantitative approach to extract the hole density imbalance between the two valleys. We find that the density difference can easily achieve more than 1011 per cm2, and it is tunable by gate voltage as well as optical excitation power. Our study highlights the response of exciton polarons to optical pumping and advances understanding of valley dependent phenomena in monolayer transition metal dichalcogenide.

Optically controlled single-valley exciton doublet states with tunable internal spin structures and spin magnetization generation

Manipulating quantum states through light-matter interactions has been actively pursued in two-dimensional materials research. Significant progress has been made toward the optical control of the valley degrees of freedom in semiconducting monolayer transition-metal dichalcogenides, based on doubly degenerate excitons from their two distinct valleys in reciprocal space. Here, we introduce a type of optically controllable doubly degenerate exciton states that come from a single valley, dubbed as single-valley exciton doublet (SVXD) states. They are unique in that their constituent holes originate from the same valence band, making possible the direct optical control of the spin structure of the excited constituent electrons. Combining ab initio GW plus Bethe-Salpeter equation (GW-BSE) calculations and a theoretical analysis method, we demonstrate such SVXD in substrate-supported monolayer bismuthene-which has been successfully grown using molecular beam epitaxy. In each of the two distinct valleys in the Brillouin zone, strong spin-orbit coupling and [Formula: see text] symmetry lead to a pair of degenerate 1s exciton states (the SVXD states) with opposite spin configurations. Any coherent linear combinations of the SVXD in a single valley can be excited by light with a specific polarization, enabling full manipulation of their internal spin configurations. In particular, a controllable net spin magnetization can be generated through light excitation. Our findings open routes to control quantum degrees of freedom, paving the way for applications in spintronics and quantum information science.

Observation of ~100% valley-coherent excitons in monolayer MoS2 through giant enhancement of valley coherence time

In monolayer transition metal dichalcogenide semiconductors, valley coherence degrades rapidly due to a combination of fast scattering and inter-valley exchange interaction. This leads to a sub-picosecond valley coherence time, making coherent manipulation of exciton a highly challenging task. Using monolayer MoS2 sandwiched between top and bottom graphene, here we demonstrate fully valley-coherent excitons by observing ~100% degree of linear polarization in steady state photoluminescence. This is achieved in this unique design through a combined effect of (a) suppression in exchange interaction due to enhanced dielectric screening, (b) reduction in exciton lifetime due to a fast inter-layer transfer to graphene, and (c) operating in the motional narrowing regime. We disentangle the role of the key parameters affecting valley coherence by using a combination of calculation (solutions of Bethe-Salpeter and Maialle-Silva-Sham equations) and a careful choice of design of experiments using four different stacks with systematic variation of screening and exciton lifetime. To the best of our knowledge, this is the first report in which the excitons are found to be valley coherent in the entire lifetime in monolayer semiconductors, allowing optical readout of valley coherence possible.

Andreev reflection between aluminum and graphene across van der Waals barriers

We present planar aluminum superconductor–graphene junctions whose hybrid interface is engineered for couplings ranging from tunneling to the strongly coupled regime by employing an atomically thin van der Waals tunneling barrier. Without the vdW barrier, we find Al makes strongly coupled contacts with the fully proximities graphene channel underneath. Using a large band gap hexagonal boron nitride (hBN) barrier, we find the junctions always remain in the weak coupling regime, exhibiting tunneling characteristics. Using monolayer semi-conducting transition metal dichalcogenides (TMDs) such as MoS2, we realize intermediate coupling with enhanced junction conductance due to the Andreev process. In this intermediate regime, we find that junction resistance changes in discrete steps when sweeping a perpendicular magnetic field. The period of the resistance steps in the magnetic field is inversely proportional to the junction area, suggesting the physical origin of our observations is due to magnetic-field-induced vortex formation in the planar junction.

Every-other-layer dipolar excitons in a spin-valley locked superlattice.

Monolayer semiconducting transition metal dichalcogenides possess broken inversion symmetry and strong spin-orbit coupling, leading to a unique spin-valley locking effect. In 2H stacked pristine multilayers, spin-valley locking yields an electronic superlattice structure, where alternating layers correspond to barriers and quantum wells depending on the spin-valley indices. Here we show that the spin-valley locked superlattice hosts a kind of dipolar exciton with the electron and hole constituents separated in an every-other-layer configuration: that is, either in two even or two odd layers. Such excitons become optically bright via hybridization with intralayer excitons. This effect is also manifested by the presence of multiple anti-crossing patterns in the reflectance spectra, as the dipolar exciton is tuned through the intralayer resonance by an electric field. The reflectance spectra further reveal an excited state orbital of the every-other-layer exciton, pointing to a sizable binding energy in the same order of magnitude as the intralayer exciton. As layer thickness increases, the dipolar exciton can form a one-dimensional Bose-Hubbard chain displaying layer number-dependent fine spectroscopy structures.

Valley selectivity of soft x-ray excitations of core electrons in two-dimensional transition metal dichalcogenides

Optical properties of semiconducting monolayer transition metal dichalcogenides have received a lot of attention in recent years, following the discovery of the valley selective optical population of either ${\text{K}}_{+}$ or ${\text{K}}_{\ensuremath{-}}$ valleys at the direct band gap, depending on the polarization of the incoming light. We use group theoretical selection rules, as well as ab initio DFT calculations, to investigate whether this valley selectivity effect is also present in x-ray optical transitions from the flat core level of the transition metal atom to the valence and conduction band K valleys. Valley selectivity is predicted for $s, {p}_{1/2}$, and ${p}_{3/2}$ edges in transitions to and from the valence band edges with circularly polarized radiation. Possible novel applications to the diagnostics of valleytronic properties and intervalley dynamics are investigated and the feasibility of ultrafast pump-probe and Kerr rotations experiments with suitable soft-x-ray free-electron laser sources is discussed.

Band Alignment Engineering by Twist Angle and Composition Modulation for Heterobilayer.

Atomically thin monolayer semiconducting transition metal dichalcogenides (TMDs), exhibiting direct band gap and strong light-matter interaction, are promising for optoelectronic devices. However, an efficient band alignment engineering method is required to further broaden their practical applications as versatile optoelectronics. In this work, the band alignment of two vertically stacked monolayer TMDs using the chemical vapor deposition (CVD) method is effectively tuned by two strategies: 1) formulating the compositions of MoS2(1-x) Se2x alloys, and 2) varying the twist angles of the stacked heterobilayer structures. Photoluminescence (PL) results combined with density functional theory (DFT) calculation show that by changing the alloy composition, a continuously tunable band alignment and a transition of type II-type I-type II band alignment of TMD heterobilayer is achieved. Moreover, only at moderate (10°-50°) twist angles, a PL enhancement of 28%-110% caused by the type I alignment is observed, indicating that the twist angle is coupled with the global band structure of heterobilayer. A heterojunction device made with MoS0.76 Se1.24 /WS2 of 14° displays a significantly high photoresponsivity (55.9 AW-1 ), large detectivity (1.07 × 1010 Jones), and high external quantum efficiency (135%). These findings provide engineering tools for heterostructure design for their application in optoelectronic devices.

Effect of intravalley and intervalley electron-hole exchange on the nonlinear optical response of monolayer MoSe2

The coherent third-order nonlinear response of monolayer transition-metal dichalcogenide semiconductors, such as ${\mathrm{MoSe}}_{2}$, is dominated by the nonlinear exciton response, as well as biexciton and trion resonances. The fact that these resonances may be spectrally close together makes identification of the signatures, for example in differential transmission (DT), challenging. Instead of focusing on explaining a given set of experimental data, a systematic study aimed at elucidating the roles of intravalley and intervalley long-range electron-hole $(e\ensuremath{-}\mathrm{h})$ exchange on the DT spectra is presented. Previous works have shown that the $e\ensuremath{-}\mathrm{h}$ long-range exchange introduces a linear leading-order term in the exciton dispersion. Based on a generalized Lippmann-Schwinger equation, we show that the presence of this linear dispersion term can reduce the biexciton binding energy to zero, contrary to the conventional situation of quadratic dispersion where an arbitrarily weak (well-behaved) attractive interaction always supports bound state(s). The effects of spin scattering and the spin-orbit interaction caused by $e\ensuremath{-}\mathrm{h}$ exchange are also clarified, and the DT line shape at the exciton and trion resonance is studied as a function of $e\ensuremath{-}\mathrm{h}$ exchange strength. In particular, as the exciton line shape is determined by the interplay of linear exciton susceptibility and the bound-state two-exciton resonance in the $T$ matrix, the line shape at the trion is similarly determined by the interplay of the linear trion susceptibility and the bound-state exciton-trion resonance in the $T$ matrix.

Many-Body Exciton and Intervalley Correlations in Heavily Electron-Doped WSe2 Monolayers

In monolayer transition-metal dichalcogenide semiconductors, many-body correlations can manifest in optical spectra when electron-hole pairs (excitons) are photoexcited into a 2D Fermi sea of mobile carriers. At low carrier densities, the formation of charged excitons (X±) is well documented. However, in WSe2 monolayers, an additional absorption resonance, often called X-', emerges at high electron density. Its origin is not understood. Here, we investigate the X-' state via polarized absorption spectroscopy of gated WSe2 monolayers in magnetic fields to 60T. Field-induced filling and emptying of the lowest optically active Landau level in the K' valley causes repeated quenching of the corresponding optical absorption. Surprisingly, these quenchings are accompanied by absorption changes to higher Landau levels in both K' and K valleys, which are unoccupied. These results cannot be reconciled within a single-particle picture, and demonstrate the many-body nature and intervalley correlations of the X-' quasiparticle state.

Ultralow contact resistance between semimetal and monolayer semiconductors.

Advanced beyond-silicon electronic technology requires both channel materials and also ultralow-resistance contacts to be discovered1,2. Atomically thin two-dimensional semiconductors have great potential for realizing high-performance electronic devices1,3. However, owing to metal-induced gap states (MIGS)4-7, energy barriers at the metal-semiconductor interface-which fundamentally lead to high contact resistance and poor current-delivery capability-have constrained the improvement of two-dimensional semiconductor transistors so far2,8,9. Here we report ohmic contact between semimetallic bismuth and semiconducting monolayer transition metal dichalcogenides (TMDs) where the MIGS are sufficiently suppressed and degenerate states in the TMD are spontaneously formed in contact with bismuth. Through this approach, we achieve zero Schottky barrier height, a contact resistance of 123ohmmicrometres and an on-state current density of 1,135microampsper micrometre on monolayer MoS2; these two values are, to the best of our knowledge, the lowest and highest yet recorded, respectively. We also demonstrate that excellent ohmic contacts can be formed on various monolayer semiconductors, including MoS2, WS2 and WSe2. Our reported contact resistances are a substantial improvement for two-dimensional semiconductors, and approach the quantum limit. This technology unveils the potential of high-performance monolayer transistors that are on par with state-of-the-art three-dimensional semiconductors, enabling further device downscaling and extending Moore's law.

Valley relaxation of resident electrons and holes in a monolayer semiconductor: Dependence on carrier density and the role of substrate-induced disorder

Using time-resolved optical Kerr rotation, we measure the low temperature valley dynamics of resident electrons and holes in exfoliated WSe$_2$ monolayers as a systematic function of carrier density. In an effort to reconcile the many disparate timescales of carrier valley dynamics in monolayer semiconductors reported to date, we directly compare the doping-dependent valley relaxation in two electrostatically-gated WSe$_2$ monolayers having different dielectric environments. In a fully-encapsulated structure (hBN/WSe$_2$/hBN, where hBN is hexagonal boron nitride), valley relaxation is found to be monoexponential. The valley relaxation time $\tau_v$ is quite long ($\sim$10~$\mu$s) at low carrier densities, but decreases rapidly to less than 100~ns at high electron or hole densities $\gtrsim$2 $\times 10^{12}$~cm$^{-2}$. In contrast, in a partially-encapsulated WSe$_2$ monolayer placed directly on silicon dioxide (hBN/WSe$_2$/SiO$_2$), carrier valley relaxation is multi-exponential at low carrier densities. The difference is attributed to environmental disorder from the SiO$_2$ substrate. Unexpectedly, very small out-of-plane magnetic fields can increase $\tau_v$, especially in the hBN/WSe$_2$/SiO$_2$ structure, suggesting that localized states induced by disorder can play an important role in depolarizing spins and mediating the valley relaxation of resident carriers in monolayer transition metal-dichalcogenide semiconductors.

Valley pseudospin relaxation of charged excitons in monolayer MoTe2

Zeeman effect induced by the magnetic field introduces a splitting between the two valleys at K + and K − points of the Brillouin zone in monolayer semiconducting transition metal dichalcogenides. In consequence, the photoluminescence signal exhibits a field dependent degree of circular polarization. We present a comprehensive study of this effect in the case of a trion in monolayer MoTe2, showing that although time integrated data allows us to deduce a g-factor of the trion state, such an analysis cannot be substantiated by the timescales revealed in the time-resolved experiments.

Coulomb-engineered heterojunctions and dynamical screening in transition metal dichalcogenide monolayers

The manipulation of two-dimensional materials via their dielectric environment offers novel opportunities to control electronic as well as optical properties and allows to imprint nanostructures in a non-invasive way. Here we asses the potential of monolayer semiconducting transition metal dichalcogenides (TMDCs) for Coulomb engineering in a material realistic and quantitative manner. We compare the response of different TMDC materials to modifications of their dielectric surrounding, analyze effects of dynamic substrate screening, i.e. frequency dependencies in the dielectric functions, and discuss inherent length scales of Coulomb-engineered heterojunctions. We find symmetric and rigid-shift-like quasi-particle band-gap modulations for both, instantaneous and dynamic substrate screening. From this we derive short-ranged self energies for an effective multi-scale modeling of Coulomb engineered heterojunctions composed of an homogeneous monolayer placed on a spatially structured substrate. For these heterojunctions, we show that band gap modulations on the length scale of a few lattice constants are possible rendering external limitations of the substrate structuring more important than internal effects. We find that all semiconducting TMDCs are similarly well suited for these external and non-invasive modifications.

Ground and excited state exciton polarons in monolayer MoSe2.

Monolayer transition metal dichalcogenide semiconductors, with versatile experimentally accessible exciton species, offer an interesting platform for investigating the interaction between excitons and a Fermi sea of charges. Using hexagonal boron nitride encapsulated monolayer MoSe2, we study the impact of charge density tuning on the A and B series of exciton Rydberg states, including A:1s, A:2s, B:1s, and B:2s. The doping dependence of the A:2s state provides an opportunity to examine such interactions with greatly reduced exciton binding energy and more spatially diffuse structures, and we found that the impact of the Fermi sea becomes much more dramatic compared to the A:1s state. Using photoluminescence upconversion, we verify that the B:2s exciton state displays similar behavior when interacting with the Fermi sea despite being well above the bare bandgap in energy. Photoluminescence and reflection spectra of the A:1s state show clear evidence that the interaction of the exciton with a Fermi sea is best described by the exciton-polaron model, rather than a trion model. Our experimental results demonstrate that overall features of charge interaction are quite generic and highly robust, offering key insights into the dressed many body states in a Fermi sea.

Transient absorption of transition metal dichalcogenide monolayers studied by a photodope-pump-probe technique

We report three-pulse photodope-pump-probe measurements on photocarrier dynamics in semiconducting transition metal dichalcogenide monolayers of ${\mathrm{MoS}}_{2}$, ${\mathrm{WS}}_{2}$, ${\mathrm{MoSe}}_{2}$, and ${\mathrm{WSe}}_{2}$. The samples are fabricated by metal-organic chemical vapor deposition and mechanical exfoliation techniques and characterized by photoluminescence spectroscopy. In the time-resolved measurement, the samples are first photodoped by a prepulse, which injects background photocarriers of various densities. A pump pulse then injects photocarriers, whose dynamics is monitored by measuring a differential reflection of a time-delayed probe pulse. We found that the ultrafast decay component of the differential reflection signal, which has been widely reported before, shows minimal dependence on the background exciton density. This observation shows that a previously suggested carrier-trapping model cannot account for this component. The results thus further support an exciton-formation model that was previously proposed based on spectroscopic evidence.

Photoactivation of Strong Photoluminescence in Superacid-Treated Monolayer Molybdenum Disulfide.

To advance the development of atomically thin optoelectronics using two-dimensional (2D) materials, engineering strong luminescence with a physicochemical basis is crucial. Semiconducting monolayer transition-metal dichalcogenides (TMDCs) are candidates for this, but their quantum yield (QY) is known to be poor. Recently, a molecular superacid treatment of bis(trifluoromethane)sulfonimide (TFSI) generated unambiguously bright monolayer TMDCs and a high QY. However, this method is highly dependent on the processing conditions and therefore has not been generalized. Here, we shed light on environmental factors to activate the photoluminescence (PL) intensity of the TFSI-treated monolayer MoS2, with a factor of more than 2 orders of magnitude greater than the original by photoactivation. The method is useful for both mechanically exfoliated and chemically deposited samples. The existence of photoirradiation larger than the band gap demonstrates enhancement of the PL of MoS2; on the other hand, activation by thermal annealing, as demonstrated in the previous report, is less effective for enhancing the PL intensity. The photoactivated monolayer MoS2 shows a long lifetime of ∼1.35 ns, more than a 30-fold improvement over the original as exfoliated. The consistent realization of the bright monolayer MoS2 reveals that air exposure is an essential factor in the process. TFSI treatment in a N2 environment was not effective for achieving a strong PL, even after the photoactivation. These findings can serve as a basis for engineering the bright atomically thin materials for 2D optoelectronics.

(Invited) Wafer-Scale Epitaxy of Transition Metal Dichalcogenides By MOCVD

Monolayer semiconducting transition metal dichalcogenides (MX2, M=W, Mo and X=S, Se) exhibit novel electronic and optical properties. Availability of epitaxial single-crystal monolayers over a wafer scale is a major hurdle in integrating these materials with existing device fabrication processes. Our approach focusses on synthesis of these monolayers using gas source precursors, like those used in traditional III-V semiconductor industry. The precursors are kept in temperature and pressure-controlled bubblers outside the growth chamber and can be metered independently into the growth zone with precision. Uniform epitaxial binary TMD monolayers including MoS2, WS2, WSe2 and MoSe2 have been deposited on 2” sapphire wafers in a cold-wall CVD reactor using metal hexacarbonyl and hydride chalcogen precursors. A multi-step growth process comprising of precursor modulation was developed for WSe2 to independently control nucleation density and the lateral growth rate of monolayer domains on the sapphire substrate [1]. For the sulfides, additional temperature modulation was introduced to increase crystalline quality. Using this approach, uniform, coalesced monolayer and few-layer TMD films were obtained on 2” sapphire substrates. In-plane X-ray diffraction demonstrates that the films are epitaxially oriented with respect to sapphire with narrow X-ray full-width-at-half-maximum indicating minimal rotational misorientation of domains within the basal plane [2]. Deposition of these materials in the same reactor provides insight into the factors controlling their growth, which in essential for the growth of heterostructures and/or alloys. Transmission electron microscopy analysis of these materials revealed additional information about the coalesced film structure. For instance, ~95 % single oriented WS2 domains were observed when the film growth rate was modulated. For WS2, it was also confirmed that despite translational line defects present in the film, mirror boundaries were predominantly absent. WS2 also showed no defect related photoluminescence peak at 80 K, indicating its high quality.In this talk the factors affecting the growth of TMDs (MX2, M=W, Mo and X=S, Se) will be presented. The role of the substrate surface in the nucleation and growth of these TMDs will be discussed. In addition, the structural and optoelectronic characteristics for these films will also be presented.The authors acknowledge financial support of the U.S. National Science Foundation through the Penn State 2D Crystal Consortium – Materials Innovation Platform (2DCC-MIP) under NSF cooperative agreement DMR-1539916 and EFRI 2-DARE Grant EFRI-1433378.[1] Zhang X, Choudhury TH, Chubarov M et al., 2018. Nano Lett. 18(2):1049–56[2] Chubarov M, Choudhury TH, Zhang X et al., 2018. Nanotechnology. 29(5):55706

Band Filling and Cross Quantum Capacitance in Ion-Gated Semiconducting Transition Metal Dichalcogenide Monolayers.

Ionic liquid gated field-effect transistors (FETs) based on semiconducting transition metal dichalcogenides (TMDs) are used to study a rich variety of extremely interesting physical phenomena, but important aspects of how charge carriers are accumulated in these systems are not understood. We address these issues by means of a systematic experimental study of transport in monolayer MoSe2 and WSe2 as a function of magnetic field and gate voltage, exploring accumulated densities of carriers ranging from approximately 1014 cm-2 holes in the valence band to 4 × 1014 cm-2 electrons in the conduction band. We identify the conditions when the chemical potential enters different valleys in the monolayer band structure (the K and Q valley in the conduction band and the two spin-split K-valleys in the valence band) and find that an independent electron picture describes the occupation of states well. Unexpectedly, however, the experiments show very large changes in the device capacitance when multiple valleys are occupied that are not at all compatible with the commonly expected quantum capacitance contribution of these systems, CQ = e2/ (dμ/dn). A theoretical analysis of all terms responsible for the total capacitance shows that under general conditions a term is present besides the usual quantum capacitance, which becomes important for very small distances between the capacitor plates. This term, which we call cross quantum capacitance, originates from screening of the electric field generated by charges on one plate from charges sitting on the other plate. The effect is negligible in normal capacitors but large in ionic liquid FETs because of the atomic proximity between the ions in the gate and the accumulated charges on the TMD, and it accounts for all our experimental observations. Our findings therefore reveal an important contribution to the capacitance of physical systems that had been virtually entirely neglected until now.