K-? crossover transition in the conduction band of monolayer MoS2 under hydrostatic pressure.
ABSTRACT: Monolayer MoS2 is a promising material for optoelectronics applications owing to its direct bandgap, enhanced Coulomb interaction, strong spin-orbit coupling, unique valley pseudospin degree of freedom, etc. It can also be implemented for novel spintronics and valleytronics devices at atomic scale. The band structure of monolayer MoS2 is well known to have a direct gap at K (K') point, whereas the second lowest conduction band minimum is located at ? point, which may interact with the valence band maximum at K point, to make an indirect optical bandgap transition. We experimentally demonstrate the direct-to-indirect bandgap transition by measuring the photoluminescence spectra of monolayer MoS2 under hydrostatic pressure at room temperature. With increasing pressure, the direct transition shifts at a rate of 49.4 meV/GPa, whereas the indirect transition shifts at a rate of -15.3 meV/GPa. We experimentally extract the critical transition point at the pressure of 1.9 GPa, in agreement with first-principles calculations. Combining our experimental observation with first-principles calculations, we confirm that this transition is caused by the K-? crossover in the conduction band.
Project description:The layered transition metal dichalcogenides have attracted considerable interest for their unique electronic and optical properties. While the monolayer MoS2 exhibits a direct bandgap, the multilayer MoS2 is an indirect bandgap semiconductor and generally optically inactive. Here we report electric-field-induced strong electroluminescence in multilayer MoS2. We show that GaN-Al2O3-MoS2 and GaN-Al2O3-MoS2-Al2O3-graphene vertical heterojunctions can be created with excellent rectification behaviour. Electroluminescence studies demonstrate prominent direct bandgap excitonic emission in multilayer MoS2 over the entire vertical junction area. Importantly, the electroluminescence efficiency observed in multilayer MoS2 is comparable to or higher than that in monolayers. This strong electroluminescence can be attributed to electric-field-induced carrier redistribution from the lowest energy points (indirect bandgap) to higher energy points (direct bandgap) in k-space. The electric-field-induced electroluminescence is general for other layered materials including WSe2 and can open up a new pathway towards transition metal dichalcogenide-based optoelectronic devices.
Project description:Two-dimensional layered transition metal dichalcogenides (TMDCs) show great potential for optoelectronic devices due to their electronic and optical properties. A metal-semiconductor interface, as epitaxial graphene - molybdenum disulfide (MoS2), is of great interest from the standpoint of fundamental science, as it constitutes an outstanding platform to investigate the interlayer interaction in van der Waals heterostructures. Here, we study large area MoS2-graphene-heterostructures formed by direct transfer of chemical-vapor deposited MoS2 layer onto epitaxial graphene/SiC. We show that via a direct transfer, which minimizes interface contamination, we can obtain high quality and homogeneous van der Waals heterostructures. Angle-resolved photoemission spectroscopy (ARPES) measurements combined with Density Functional Theory (DFT) calculations show that the transition from indirect to direct bandgap in monolayer MoS2 is maintained in these heterostructures due to the weak van der Waals interaction with epitaxial graphene. A downshift of the Raman 2D band of the graphene, an up shift of the A1g peak of MoS2 and a significant photoluminescence quenching are observed for both monolayer and bilayer MoS2 as a result of charge transfer from MoS2 to epitaxial graphene under illumination. Our work provides a possible route to modify the thin film TDMCs photoluminescence properties via substrate engineering for future device design.
Project description:Monolayer transition metal dichalcogenides, such as MoS2 and WSe2, have been known as direct gap semiconductors and emerged as new optically active materials for novel device applications. Here we reexamine their direct gap properties by investigating the strain effects on the photoluminescence of monolayer MoS2 and WSe2. Instead of applying stress, we investigate the strain effects by imaging the direct exciton populations in monolayer WSe2-MoS2 and MoSe2-WSe2 lateral heterojunctions with inherent strain inhomogeneity. We find that unstrained monolayer WSe2 is actually an indirect gap material, as manifested in the observed photoluminescence intensity-energy correlation, from which the difference between the direct and indirect optical gaps can be extracted by analyzing the exciton thermal populations. Our findings combined with the estimated exciton binding energy further indicate that monolayer WSe2 exhibits an indirect quasiparticle gap, which has to be reconsidered in further studies for its fundamental properties and device applications.Monolayer transition metal dichalcogenides have so far been thought to be direct bandgap semiconductors. Here, the authors revisit this assumption and find that unstrained monolayer WSe2 is an indirect-gap material, as evidenced by the observed photoluminescence intensity-energy correlation.
Project description:Two-dimensional (2D) materials beyond graphene have attracted considerable interest because of the zero bandgap drawbacks of graphene. Transition metal dichalcogenides (TMDs), such as MoS2 and WSe2, are the potential candidates for next 2D materials because atomically thin layers of TMDs exhibit unique and versatile electrical and optical properties. Although bulk TMDs materials have an indirect bandgap, an indirect-to-direct bandgap transition is observed in monolayers of TMDs (MoS2, WSe2, and MoSe2). Optical properties of TMD films can be improved by the introduction of structural defects. For example, large-area spatial tuning of the optical transition of bulk MoS2 films is achieved by using an anodic aluminum oxide (AAO) template to induce structural defects such as edge- and terrace-terminated defects in a nanomesh structure. Strong photoluminescence emission peaks with a band gap of 1.81?eV are observed, possibly because of radiative transition at the defect sites. This work shows that the AAO template lithography method has potential for the production of homogenous large-scale nanomesh structures for practical semiconductor processing applications in future MoS2-based electronic and optical devices.
Project description:The electronic band structure of MoS2, MoSe2, WS2, and WSe2, crystals has been studied at various hydrostatic pressures experimentally by photoreflectance (PR) spectroscopy and theoretically within the density functional theory (DFT). In the PR spectra direct optical transitions (A and B) have been clearly observed and pressure coefficients have been determined for these transitions to be: αA = 2.0 ± 0.1 and αB = 3.6 ± 0.1 meV/kbar for MoS2, αA = 2.3 ± 0.1 and αB = 4.0 ± 0.1 meV/kbar for MoSe2, αA = 2.6 ± 0.1 and αB = 4.1 ± 0.1 meV/kbar for WS2, αA = 3.4 ± 0.1 and αB = 5.0 ± 0.5 meV/kbar for WSe2. It has been found that these coefficients are in an excellent agreement with theoretical predictions. In addition, a comparative study of different computational DFT approaches has been performed and analyzed. For indirect gap the pressure coefficient have been determined theoretically to be -7.9, -5.51, -6.11, and -3.79, meV/kbar for MoS2, MoSe2, WS2, and WSe2, respectively. The negative values of this coefficients imply a narrowing of the fundamental band gap with the increase in hydrostatic pressure and a semiconductor to metal transition for MoS2, MoSe2, WS2, and WSe2, crystals at around 140, 180, 190, and 240 kbar, respectively.
Project description:Two-dimensional (2D) transition-metal dichalcogenides (TMDs), most notably, MoS2 and WS2, have attracted significant attention due to their sizable and direct bandgap characteristics. Although several interesting MoS2 and WS2-based optoelectronic devices have been reported, their processability and reproducibility are limited since their electrical properties are strongly dependent of the number of layers, strain and sample sizes. It is highly desirable to have a robust direct bandgap TMD, which is insensitive to those factors. In this work, using density functional theory, we explore the effects of layer number, strain and ribbon width on the electronic properties of ReS2, a new member in the TMD family. The calculation results reveal that for monolayer ReS2, the nature (direct versus indirect) and magnitude of its bandgap are insensitive to strain. Importantly, the predicted bandgap and also charge carrier mobilities are nearly independent of the number of layers. In addition, the direct bandgap of ReS2 nanoribbons is only weakly dependent on their width. These robust characteristics strongly suggest that ReS2 has great potential for applications in optoelectronic nanodevices.
Project description:Time-reversal symmetry and broken spin degeneracy enable the exploration of spin and valley quantum degrees of freedom in monolayer transition-metal dichalcogenides. While the strength of the large spin splitting in the valance band of these materials is now well-known, probing the 10-100 times smaller splitting in the conduction band poses significant challenges. Since it is easier to achieve n-type conduction in most of them, resolving the energy levels in the conduction band is crucial for the prospect of developing new spintronic and valleytronic devices. Here, we study quantum transport in high mobility monolayer MoS2 devices where we observe well-developed quantized conductance in multiples of e 2/h in zero magnetic field. We extract a sub-band spacing energy of 0.8?meV. The application of a magnetic field gradually increases the interband spacing due to the valley-Zeeman effect. Here, we extract a g-factor of ~2.16 in the conduction band of monolayer MoS2.
Project description:In emerging optoelectronic applications, such as water photolysis, exciton fission and novel photovoltaics involving low-dimensional nanomaterials, hot-carrier relaxation and extraction mechanisms play an indispensable and intriguing role in their photo-electron conversion processes. Two-dimensional transition metal dichalcogenides have attracted much attention in above fields recently; however, insight into the relaxation mechanism of hot electron-hole pairs in the band nesting region denoted as C-excitons, remains elusive. Using MoS2 monolayers as a model two-dimensional transition metal dichalcogenide system, here we report a slower hot-carrier cooling for C-excitons, in comparison with band-edge excitons. We deduce that this effect arises from the favourable band alignment and transient excited-state Coulomb environment, rather than solely on quantum confinement in two-dimension systems. We identify the screening-sensitive bandgap renormalization for MoS2 monolayer/graphene heterostructures, and confirm the initial hot-carrier extraction for the C-exciton state with an unprecedented efficiency of 80%, accompanied by a twofold reduction in the exciton binding energy.
Project description:A robust and reliable method for enhancing the photoluminescence (PL) of multilayer MoS2 is demonstrated using an oxygen plasma treatment process followed by laser exposure. Here, the plasma and laser treatments result in an indirect-to-direct band gap transition. The oxygen plasma creates a slight decoupling of the layers and converts some of the MoS2 to MoO3. Subsequent laser irradiation further oxidizes the MoS2 to MoO3, as confirmed via X-ray photoelectron spectroscopy, and results in localized regions of brightly luminescent MoS2 monolayer triangular islands as seen in high-resolution transmission electron microscopy images. The PL lifetimes are found to decrease from 494 to 190 ps after plasma and laser treatment, reflecting the smaller size of the MoS2 grains/regions. Atomic force microscopic imaging shows a 2 nm increase in thickness of the laser-irradiated regions, which provides further evidence of the MoS2 being converted to MoO3.
Project description:Monolayer transition metal dichalcogenides (TMDs) and their van der Waals heterostructures have been experimentally and theoretically demonstrated as potential candidates for photovoltaic and optoelectronic devices due to the suitable bandgap and excellent light absorption. In this work, we report the observation of photodiode behavior in (both n- and p- type) silicon/monolayer MoS2 vertical heterostructures. The photocurrent and photoresponsivity of heterostructures photodiodes were dependent both on the incident light wavelength and power density, and the highest photoresponsivity of 7.2 A/W was achieved in n-Si/monolayer MoS2 vertical heterostructures photodiodes. Compared with n-Si/MoS2 heterostructures, the photoresponsivity of p-Si/MoS2 heterostructure was much lower. Kelvin probe microscope (KFM) results demonstrated the more efficient separation of photogenerated excitons in n-Si/MoS2 than that in p-Si/MoS2. Coupling KFM results with band alignments of (p-, n-) Si/MoS2 heterostructures, the origins of photodiode-like phenomena of p-Si/MoS2 and n-Si/MoS2 have been unveiled, that is intrinsic built-in electric field in p-n junction, and modulated barrier height and width at the interface in n-n junction. Our work may benefit to the deep understanding of the integration of two-dimensional materials with more conventional three-dimensional semiconductors, and then contribute to the developments in the area of van der Waals heterostructures.