Prototypical Transition Metal Dichalcogenide Research Articles

Effects of hot phonons and thermal stress in micro-Raman spectra of molybdenum disulfide

Micro-Raman spectroscopy has become an important tool in probing thermophysical properties in functional materials. Localized heating by the focused Raman excitation laser beam can produce both stress and local nonequilibrium phonons in the material. Here, we investigate the effects of hot optical phonons in the Raman spectra of molybdenum disulfide and distinguish them from those caused by thermally induced compressive stress, which causes a Raman frequency blue shift. We use a thermomechanical analysis to correct for this stress effect in the equivalent lattice temperature extracted from the measured Raman peak shift. When the heating Gaussian laser beam is reduced to 0.71 μm, the corrected peak shift temperature rise is 17% and 8%, respectively, higher than those determined from the measured peak shift and linewidth without the stress correction, and 32% smaller than the optical phonon temperature rise obtained from the anti-Stokes to Stokes intensity ratio. This nonequilibrium between the hot optical phonons and the lattice vanishes as the beam width increases to 1.53 μm. Much less pronounced than those reported in prior micro-Raman measurements of suspended graphene, this observed hot phonon behavior agrees with a first-principles based multitemperature model of overpopulated zone-center optical phonons compared to other optical phonons in the Brillouin zone and acoustic phonons of this prototypical transition metal dichalcogenide. The findings provide detailed insight into the energy relaxation processes in this emerging electronic and optoelectronic material and clarify an important question in micro-Raman measurements of thermal transport in this and other two-dimensional materials.

Apparent differences between single layer molybdenum disulphide fabricated via chemical vapour deposition and exfoliation

Innovative applications based on two-dimensional solids require cost-effective fabrication processes resulting in large areas of high quality materials. Chemical vapour deposition is among the most promising methods to fulfill these requirements. However, for 2D materials prepared in this way it is generally assumed that they are of inferior quality in comparison to the exfoliated 2D materials commonly used in basic research. In this work we challenge this assumption and aim to quantify the differences in quality for the prototypical transition metal dichalcogenide MoS2. To this end single layers of MoS2 prepared by different techniques (exfoliation, grown by different chemical vapour deposition methods, transfer techniques and as vertical heterostructure with graphene) are studied by Raman and photoluminescence spectroscopy, complemented by atomic force microscopy. We demonstrate that as-prepared MoS2, directly grown on SiO2, differs from exfoliated MoS2 in terms of higher photoluminescence, lower electron concentration and increased strain. As soon as a water film is intercalated (e.g. by transfer) underneath the grown MoS2, in particular the (opto)electronic properties become practically identical to those of exfoliated MoS2. A comparison of the two most common precursors shows that the growth with MoO3 causes greater strain and/or defect density deviations than growth with ammonium heptamolybdate. As part of a heterostructure directly grown MoS2 interacts much stronger with the substrate and in this case an intercalated water film does not lead to the complete decoupling, which is typical for exfoliation or transfer. Our work shows that the supposedly poorer quality of grown 2D transition metal dichalcogenides is indeed a misconception.

Thermally Activated Gold‐Mediated Transition Metal Dichalcogenide Exfoliation and a Unique Gold‐Mediated Transfer

Layered materials like transition metal dichalcogenides (TMDCs) enable exciting new physics in their 2D limit. Combined with successful demonstrations of 2D transistors and devices, the need for high‐quality large‐scale monolayers increases. In this light, scalable gold‐mediated exfoliations attract broad attention to supersede the traditional scotch tape method as a means for high‐quality materials. Gold proved to be suitably adhesive for the exfoliation of several 2D materials, including TMDCs. Previously reported methods rely on a simple press and peel mechanism. However, herein, a gold‐mediated exfoliation enabled by low‐temperature annealing is presented for the first time. This simple modification potentially increases the range of external conditions under which gold‐mediated exfoliations operate in a robust manner. The exfoliation achieves scaling with parent crystal areas, rendering it on par with previously reported methods. On top of that, a unique gold‐mediated transfer concept is introduced, where gold is repurposed as a metallic (polymer‐free) transfer membrane. The transfer allows the deterministic and clean relocation of the exfoliated monolayers onto technologically relevant substrates like SiO2/Si. The process is benchmarked using MoS2 as the prototypical TMDC and monolayer areas up to ≈80 mm2 are successfully exfoliated and transferred.

Origin and evolution of ultraflat bands in twisted bilayer transition metal dichalcogenides: Realization of triangular quantum dots

Using a multiscale computational approach, we probe the origin and evolution of ultraflatbands in moir\'e superlattices of twisted bilayer MoS$_2$, a prototypical transition metal dichalcogenide. Unlike twisted bilayer graphene, we find no unique magic angles in twisted bilayer MoS$_2$ for flatband formation. Ultraflatbands form at the valence band edge for twist angles ($\theta$) close to 0$^\circ$ and at both the valence and conduction band edges for $\theta$ close to 60$^\circ$, and have distinct origins. For$ \theta$ close to 0$^\circ$, inhomogeneous hybridization in the reconstructed moir\'e superlattice is sufficient to explain the formation of flatbands. For $\theta$ close to 60$^\circ$, additionally, local strains cause the formation of modulating triangular potential wells such that electrons and holes are spatially separated. This leads to multiple energy-separated ultraflatbands at the band edges closely resembling eigenfunctions of a quantum particle in an equilateral triangle well. Twisted bilayer transition metal dichalcogenides are thus suitable candidates for the realisation of ordered quantum dot array.

Intertwined chiral charge orders and topological stabilization of the light-induced state of a prototypical transition metal dichalcogenide

The fundamental idea that the constituents of interacting many body systems in complex quantum materials may self-organise into long range order under highly non-equilibrium conditions leads to the notion that entirely new and unexpected functionalities might be artificially created. However, demonstrating new emergent order in highly non-equilibrium transitions has proven surprisingly difficult. In spite of huge recent advances in experimental ultrafast time-resolved techniques, methods that average over successive transition outcomes have so far proved incapable of elucidating the emerging spatial structure. Here, using scanning tunneling microscopy, we report for the first time the charge order emerging after a single transition outcome initiated by a single optical pulse in a prototypical two-dimensional dichalcogenide 1T-TaS2. By mapping the vector field of charge displacements of the emergent state, we find surprisingly intricate, long-range, topologically non-trivial charge order in which chiral domain tiling is intertwined with unpaired dislocations which play a crucial role in enhancing the emergent states’ remarkable stability. The discovery of the principles that lead to metastability in charge-ordered systems opens the way to designing novel emergent functionalities, particularly ultrafast all-electronic non-volatile cryo-memories.

Electronic band dispersion determination in azimuthally disordered transition-metal dichalcogenide monolayers

Generally, the lack of long-range order in materials prevents from experimentally addressing their electronic band dispersion by angle-resolved photoelectron spectroscopy (ARPES), limiting such assessment to single crystalline samples. Here we demonstrate that the ARPES spectra of azimuthally disordered transition metal dichalcogenide (TMDC) monolayers with 2 H phase are dominated by their band dispersion along the two high symmetry directions Γ-K and Γ-M. We exemplify this by analyzing the ARPES spectra of four prototypical TMDCs within a mathematical framework, which allows to consistently explain the reported observations. A robust base for investigating TMDC monolayers significantly beyond single crystal samples is thus established.

Ultraflatbands and Shear Solitons in Moiré Patterns of Twisted Bilayer Transition Metal Dichalcogenides.

Ultraflatbands in twisted bilayers of two-dimensional materials have the potential to host strong correlations, including the Mott-insulating phase at half-filling of the band. Using first-principles density functional theory calculations, we show the emergence of ultraflatbands at the valence band edge in twisted bilayer MoS_{2}, a prototypical transition metal dichalcogenide. The computed band widths, 5 and 23meV for 56.5° and 3.5° twist angles, respectively, are comparable to that of twisted bilayer graphene near "magic" angles. Large structural transformations in the moiré patterns lead to formation of shear solitons at stacking boundaries and strongly influence the electronic structure. We extend our analysis for twisted bilayer MoS_{2} to show that flatbands can occur at the valence band edge of twisted bilayer WS_{2}, MoSe_{2}, and WSe_{2} as well.

Controlling the surface photovoltage on WSe2 by surface chemical modification

The surface photovoltage (SPV) effect is key to the development of opto-electronic devices such as solar-cells and photo-detectors. For the prototypical transition metal dichalcogenide WSe2, core level and valence band photoemission measurements show that the surface band bending of pristine cleaved surfaces can be readily modified by adsorption with K (an electron donor) or C60 (an electron acceptor). Time-resolved pump-probe photoemission measurements reveal that the SPV for pristine cleaved surfaces is enhanced by K adsorption, but suppressed by C60 adsorption, and yet the SPV relaxation time is substantially shortened in both cases. Evidently, adsorbate-induced electronic states act as electron-hole recombination centers that shorten the carrier lifetime.

Dielectric-MoS2 Interfaces Grown By Atomic Layer Deposition

Molybdenum disulfide (MoS2) has become a prototypical transition metal dichalcogenide (TMDC) atomic-layered material because of its unique materials properties. For example, bulk MoS2 exhibits an indirect band-gap of 1.3 eV, while a single monolayer has a direct band-gap of 1.8 eV. Recently, nanometer scale transistor devices have been made with MoS2 and graphene, yet much of this work relies on layered materials prepared using chemical vapor deposition (CVD) and mechanically exfoliation. Multiple reports have demonstrated the growth of MoS2 via CVD, but only a few studies have reported MoS2 growth using atomic layer deposition (ALD), which offers potential advantages for high volume semiconductor manufacturing. Here, we report the ALD of few-layer MoS2 films using MoF6 and various sulfur precursors on various ALD-grown dielectric surfaces and the ALD of metal oxides on the ALD MoS2 films at temperatures between 100-300 °C. In particular, we used in-situ quartz crystal microbalance measurements to investigate the nucleation of MoS2 ALD on oxide surfaces and vice versa. In general, self-limiting growth of MoS2 was observed on a wide range of dielectric surfaces including alumina, magnesia, and hafnia. The ALD MoS2 films were amorphous as-deposited, but crystallized into a layered atomic structure upon annealing at 800 °C. Using in-situ spectroscopy and electrical measurements, growth inhibition of MoS2 was seen depending on the growth substrate. These studies provide insight into the low-temperature ALD of MoS2 and provide guidance for the ALD of additional TMDC films.

Raman scattering and anomalous Stokes-anti-Stokes ratio in MoTe2 atomic layers.

Stokes and anti-Stokes Raman scattering are performed on atomic layers of hexagonal molybdenum ditelluride (MoTe2), a prototypical transition metal dichalcogenide (TMDC) semiconductor. The data reveal all six types of zone center optical phonons, along with their corresponding Davydov splittings, which have been challenging to see in other TMDCs. We discover that the anti-Stokes Raman intensity of the low energy layer-breathing mode becomes more intense than the Stokes peak under certain experimental conditions, and find the effect to be tunable by excitation frequency and number of atomic layers. These observations are interpreted as a result of resonance effects arising from the C excitons in the vicinity of the Brillouin zone center in the photon-electron-phonon interaction process.