Monolayer Two-dimensional Transition Metal Dichalcogenides Research Articles

Photon Upconversion of Defect-Bound Excitons in hBN-Encapsulated MoS2 Monolayer.

Atomic defects associated with vacancies in two-dimensional transition metal dichalcogenide monolayers efficiently trap charged carriers and strongly localize excitons. Defects in semiconducting monolayers are seldomly utilized for enhancing optical phenomena, although they may provide resonant intermediate states within the energy band gap for applications with multiphoton excitations, like highly efficient and thermally robust photon upconversion. In an MoS2 monolayer encapsulated by hBN with high defect and resident electron densities, we observe an upconversion of localized exciton (XL) emission with a huge energy gain of up to 290 meV. The upconverted XL emission is robust up to temperatures of about 120 K and exhibits a sublinear or a nearly linear laser power dependence for the energy gain of about 100 meV and above 200 meV, respectively. The upconversion mechanism is explained by a cooperative energy transfer process between the photocreated and resident electrons, in which hybridized pairs of single sulfur vacancies likely act as real intermediate states. Additionally, we find a weak upconversion of the neutral exciton photoluminescence with an energy gain of about 350 meV for quasi-resonant excitation of the XL exciton. It is attributed to a two-step, two-photon absorption.

Synthesis and Polymorph Manipulation of FeSe2 Monolayers.

Polymorph engineering involves the manipulation of material properties through controlled structural modification and is a candidate technique for creating unique two-dimensional transition metal dichalcogenide (TMDC) nanodevices. Despite its promise, polymorph engineering of magnetic TMDC monolayers has not yet been demonstrated. Here we grow FeSe2 monolayers via molecular beam epitaxy and find that they have great promise for magnetic polymorph engineering. Using scanning tunneling microscopy (STM) and spectroscopy (STS), we find that FeSe2 monolayers predominantly display a 1T' structural polymorph at 5 K. Application of voltage pulses from an STM tip causes a local, reversible transition from the 1T' phase to the 1T phase. Density functional theory calculations suggest that this single-layer structural phase transition is accompanied by a magnetic transition from an antiferromagnetic to a ferromagnetic configuration. These results open new possibilities for creating functional magnetic devices with TMDC monolayers via polymorph engineering.

A Molecular Coordination Strategy for Regulating the Interface of MoS2 Field Effect Transistors.

Chemically modifying monolayer two-dimensional transition metal dichalcogenides (TMDs) with organic molecules provides a wide range of possibilities to regulate the electronic and optoelectronic performance of both materials and devices. However, it remains challenging to chemically attach organic molecules to monolayer TMDs without damaging their crystal structures. Herein, we show that the Mo atoms of monolayer MoS2 (1L-MoS2) in defect states can coordinate with both catechol and 1,10-phenanthroline (Phen) groups, affording a facile route to chemically modifying 1L-MoS2. Through the design of two isomeric molecules (LA2 and LA5) comprising catechol and Phen groups, we show that attaching organic molecules to Mo atoms via coordinative bonds has no negative effect on the crystal structure of 1L-MoS2. Both theoretical calculation and experiment results indicate that the coordinative strategy is beneficial for (i) repairing sulfur vacancies and passivating defects; (ii) achieving a long-term and stable n-doping effect; and (iii) facilitating the electron transfer. Field effect transistors (FETs) based on the coordinatively modified 1L-MoS2 show high electron mobilities up to 120.3 cm2 V-1 s-1 with impressive current on/off ratios over 109. Our results indicate that coordinatively attaching catechol- or Phen-bearing molecules may be a general method for the nondestructive modification of TMDs.

Photoluminescence manipulation in two-dimensional transition metal dichalcogenides

Two-dimensional transition metal dichalcogenides (TMDCs) have been regarded as an intriguing platform for exploring novel physical phenomena and optoelectronic devices due to their excitonic emission characteristics derived from the atomic thin thickness and reduced dielectric screening effect. Notably, monolayer TMDCs with a direct bandgap exhibiting strong photoluminescence (PL) are promising candidates for the light-emitting devices, while the interlayer excitons in heterostructures hold great potential for the photonic chips and optical communication applications. However, the non-ideal photoluminescent intensity and quality due to the ultrathin thickness and high defect density of experimentally obtained monolayer TMDCs limit the further development for the light-emission applications. Here, we summarize the research progress on the PL manipulation of the excitonic emission in TMDCs, where the PL intensity enhancement and emission wavelength regulation are included. The concept and characteristics of excitons are overviewed firstly, followed by the discussion on the evaluation and characterization of excitonic emission. The state-of-the-art progress on the manipulation of the neutral excitons and interlayer excitons PL are then summarized. Finally, the challenges and prospects are proposed.

Photon superbunching in cathodoluminescence of excitons in WS2 monolayer

Cathodoluminescence spectroscopy in conjunction with second-order auto-correlation measurements of allows to extensively study the synchronization of photon emitters in low-dimensional structures. Co-existing excitons in two-dimensional transition metal dichalcogenide monolayers provide a great source of identical photon emitters which can be simultaneously excited by an electron. Here, we demonstrate large photon bunching with up to of a tungsten disulfide monolayer (WS2), exhibiting a strong dependence on the electron-beam current. To further improve the excitation synchronization and the electron-emitter interaction, we show exemplary that the careful selection of a simple and compact geometry—a thin, monocrystalline gold nanodisk—can be used to realize a record-high bunching of up to . This approach to control the electron excitation of excitons in a WS2 monolayer allows for the synchronization of photon emitters in an ensemble, which is important to further advance light information and computing technologies.

Wafer‐scale single‐crystalline MoSe2 and WSe2 monolayers grown by molecular‐beam epitaxy at low‐temperature — the role of island‐substrate interaction and surface steps

AbstractUltrathin two‐dimensional transition‐metal dichalcogenides (TMDs) have been pursued extensively in recent years for interesting physics and application potentials. For the latter, it is essential to synthesize crystalline TMD monolayers at wafer‐scale. Here, we report growth of single‐crystalline MSe2 (M = Mo, W) monolayers at wafer‐scale by molecular‐beam epitaxy at low temperatures (200–400°C) on nominally flat Au(1 1 1) substrates. The epifilms have low intrinsic defect densities of low 1012 cm−2. The grown films have then been exfoliated and transferred onto SiO2/Si by a wet chemical process, on which some optical measurements are performed, revealing high spatial uniformity of the samples. We also establish that MSe2 grows on Au via the van der Waals epitaxy mechanism, where a continuous film extends across the whole surface, overhangs atomic‐layer steps on substrate. We identify that the growth of highly crystalline MSe2 is promoted by an enhanced interaction between Au substrate and MSe2 islands rather than by the guidance of surface steps on substrate. The latter only arrests MSe2 lateral growth if they are multilayer high.Key points MBE growth of wafer‐scale highly crystalline TMD monolayers at low‐temperature is achieved. Island‐substrate interaction is found to play a critical role in vdW epitaxy of single‐crystalline TMDs on on‐axis substates. The TMD monolayers are of high uniformity and low intrinsic defect density.

Interaction between pentacene molecules and monolayer transition metal dichalcogenides.

Using first-principles calculations based on density-functional theory, we investigated the adsorption of pentacene molecules on monolayer two-dimensional transition metal dichalcogenides (TMD). We considered the four most popular TMDs, namely, MoS2, MoSe2, WS2 and WSe2, and we examined the structural and electronic properties of pentacene/TMD systems. We discuss how monolayer pentacene interacts with the TMDs, and how this interaction affects the charge transfer and work function of the heterostructure. We also analyse the type of band alignment formed in the heterostructure and how it is affected by molecule-molecule and molecule-substrate interactions. Such analysis is valuable since pentacene/TMD heterostructures are considered to be promising for application in flexible, thin and lightweight photovoltaics and photodetectors.

A unified approach and descriptor for the thermal expansion of two-dimensional transition metal dichalcogenide monolayers

Two-dimensional (2D) materials have enabled promising applications in modern miniaturized devices. However, device operation may lead to substantial temperature rise and thermal stress, resulting in device failure. To address such thermal challenges, the thermal expansion coefficient (TEC) needs to be well understood. Here, we characterize the in-plane TECs of transition metal dichalcogenide (TMD) monolayers and demonstrate superior accuracy using a three-substrate approach. Our measurements confirm the physical range of 2D monolayer TECs and, hence, address the more than two orders of magnitude discrepancy in literature. Moreover, we identify the thermochemical electronegativity difference of compositional elements as a descriptor, enabling the fast estimation of TECs for various TMD monolayers. Our work presents a unified approach and descriptor for the thermal expansion of TMD monolayers, which can serve as a guideline toward the rational design of reliable 2D devices.

Giant Enhancement and Directional Second Harmonic Emission from Monolayer WS2 on Silicon Substrate via Fabry-Pérot Micro-Cavity.

Two-dimensional transition metal dichalcogenides (TMDs) possess large second-order optical nonlinearity, making them ideal candidates for miniaturized on-chip frequency conversion devices, all-optical interconnection, and optoelectronic integration components. However, limited by subnanometer thickness, the monolayer TMD exhibits low second harmonic generation (SHG) conversion efficiency (<0.1%) and poor directionality, which hinders their practical applications. Herein, we proposed a Fabry-Pérot (F-P) cavity formed by coupling an atomically thin WS2 film with a silicon hole matrix to enhance the SH emission. A maximum enhancement (∼1580 times) is achieved by tuning the excitation wavelength to be resonant with the microcavity modes. The giant enhancement is attributed to the strong electric field enhancement in the F-P cavity and the oscillator strength enhancement of excitons from suspended WS2. Moreover, directional SH emission (divergence angle ∼5°) is obtained benefiting from the resonance of the F-P microcavity. Our research results can provide a practical sketch to develop both high-efficiency and directional nonlinear optical devices for silicon-based on-chip integration optics.

Computational analysis of the enhancement of photoelectrolysis using transition metal dichalcogenide heterostructures

Finding a material with all the desired properties for a photocatalytic water splitter is a challenge yet to be overcome, requiring both a surface with ideal energetics for all steps in the hydrogen and oxygen evolution reactions (HER and OER) and a bulk band gap large enough to mediate said steps. We have instead examined separating these challenges by investigating the energetic properties of two-dimensional transition metal dichalcogenides (TMDCs) that could be used as a surface coating to a material with a large enough bulk band gap. First we investigated the energetics of monolayer MoS2 and PdSe2 using density functional theory and then investigated how these energetics changed when they were combined into a heterostructure. Our results show that the surface properties were practically (0.2 eV) unchanged when combined and the MoS2 layer aligns well with the OER and HER. This work highlights the potential of TMDC monolayers as surface coatings for bulk materials that have sufficient band gaps for photocatalytic applications.

Perspective on plexciton based on transition metal dichalcogenides

Two-dimensional transition metal dichalcogenides (TMDCs) have outstanding physical advantages over graphene-like non-zero bandgap structures. It indicates that the monolayer TMDC material has significant light–material interaction, and it also implies that TMDCs have various application prospects in optoelectronic devices. The coupling of excitons and metal surface plasmons in monolayer TMDCs would affect the optical and electrical properties of the TMDC surface, and we revealed the improvement of surface catalytic reaction efficiency by plexcitons (coupling of excitons and plasmons) supported by recent experiments and theoretical reports. We also review the stress regulation on charge transfer excitons based on van der Waals (vdW) heterostructures composed of TMDCs, the special characteristics, and potential applications of coupling charge-transfer excitons with Ag plasmons in vdW and lateral heterostructures.

Enhancing excitons by oleic acid treatment in WS2, MoS2, and WS2/MoS2 heterostructure

The neutral and interlayer exciton originates from intralayer and interlayer coupling, respectively. Unlike neutral exciton, the interlayer excitons at room temperature are hard to observe and manipulate due to instability. In this work, we show the photoluminescence of WS2 and MoS2 neutral exciton can be improved by oleic acid passivation, allowing trion peaks to be observed at room temperature. More importantly, a 3-fold increase in peak intensity of interlayer excitons is achieved, and the energy peak is blue-shifted 107 meV. Our work paves the way to investigate excitons in two-dimensional transition metal dichalcogenides monolayers and heterostructures at room temperature.

Quasi-BIC-governed light absorption of monolayer transition-metal dichalcogenide-based absorber and its sensing performance

The efficiency and bandwidth of an optical absorbing material, especially for the promising two-dimensional transition metal dichalcogenides (TMDCs) are critical to underpin advances in photonic and optoelectronic devices. In this work, we present a general method to manipulate the bandwidth of an absorber with high efficiency through coupling with the quasi-bound states in the continuum (quasi-BIC). We demonstrate this strategy by taking absorbing material monolayer TMDC coupled with the lossless symmetry-broken photonic crystal (PhC) slab. An optimal-efficiency TMDC-based absorber with over three orders of magnitude of bandwidth adjustment is realized, by simultaneously adjusting the structure asymmetry parameter of PhC slab and the locations of monolayer TMDC in the structure. Interestingly, the absorption bandwidth is tailored quadratically with the asymmetry parameter, which derived from the powerful physics of bound state in the continuum (BIC) in radiation engineering. Moreover, a superior-performance optical refractive index sensor is further designed. We demonstrate that our proposed method based on quasi-BIC structure can also effectively govern the sensing performance. Present work not only provides further insight into BIC physics, but also offers a promising strategy of smart engineering in active optical devices with the properties on demand.

Nonlinear circular valley photogalvanic effect

We develop a theory of circular photogalvanic effect in nongyrotropic two-dimensional transition metal dichalcogenide monolayers under interband optical transitions. Oblique incidence of circularly polarized electromagnetic field or normal incidence of elliptically polarized electromagnetic field is assumed. In contrast to the linear-in-intensity conventional photogalvanic effect, the effect considered here arises in the second intensity order. The effect is conditioned by (i) the predominant population of the valleys by the circular in-plane electromagnetic field component and (ii) the direct drift of the photoexcited carriers by the linear-polarized in-plane electromagnetic field component in the presence of trigonal valley asymmetry.

Revealing the interrelation between C- and A-exciton dynamics in monolayer WS2 via transient absorption spectroscopy

Two-dimensional transition metal dichalcogenides (TMDs) are emerging as a promising complement for traditional semiconductor materials in ultrathin optoelectronic device fields. Developing a better understanding of high-energy C-exciton dynamics is essential for efficiently extracting hot carriers and building high-performance TMD-based light-harnessing devices; however, insight into the C-exciton dynamics remains scarce. To further understand the C-exciton dynamics, here, we have unraveled the interrelation between C-exciton and band edge A-exciton dynamics in monolayer WS2 by transient absorption spectroscopy. It is found that the band edge A-excitons could effectively generate high-energy C-excitons via the many-body process, and, in turn, the hot carriers relaxing from C-excitons to band edge states could compensate and slow the decay of the A-excitons. The comprehensive understanding of the interrelation between C-exciton and A-exciton dynamics in monolayer TMDs may trigger the potential applications for future TMD-based light-harvesting devices.

Broadband Plasmon-Enhanced Four-Wave Mixing in Monolayer MoS2.

Two-dimensional transition-metal dichalcogenide monolayers have remarkably large optical nonlinearity. However, the nonlinear optical conversion efficiency in monolayer transition-metal dichalcogenides is typically low due to small light–matter interaction length at the atomic thickness, which significantly obstructs their applications. Here, for the first time, we report broadband (up to ∼150 nm) enhancement of optical nonlinearity in monolayer MoS2 with plasmonic structures. Substantial enhancement of four-wave mixing is demonstrated with the enhancement factor up to three orders of magnitude for broadband frequency conversion, covering the major visible spectral region. The equivalent third-order nonlinearity of the hybrid MoS2-plasmonic structure is in the order of 10–17 m2/V2, far superior (∼10–100-times larger) to the widely used conventional bulk materials (e.g., LiNbO3, BBO) and nanomaterials (e.g., gold nanofilms). Such a considerable and broadband enhancement arises from the strongly confined electric field in the plasmonic structure, promising for numerous nonlinear photonic applications of two-dimensional materials.

Impurity-band optical transitions in two-dimensional Dirac materials under strain-induced synthetic magnetic field

We develop a theory of optical transitions in Coulomb impurity-doped two-dimensional transition metal dichalcogenide monolayers and study the transitions from the spin-resolved valence band to the (Coulomb) donor and acceptor impurities under the influence of a synthetic valley-selective magnetic field produced by a mechanical strain. It is shown that the optical properties of the system are determined by the strength of the synthetic magnetic field, which uncovers an experimental tool, which can be used to manipulate the properties of two-dimensional materials in valley magneto-optoelectronics.

Strain-driven phase transition and spin polarization of Re-doped transition-metal dichalcogenides.

Two-dimensional transition metal dichalcogenides (TMDCs) are promising in spintronics due to their spin-orbit coupling, but their intrinsic non-magnetic properties limit their further development. Here, we focus on the energy landscapes of TMDC (MX2, M = Mo, W and X = S, Se, Te) monolayers by rhenium (Re) substitution doping under axial strains, which controllably drive 1H ↔ 1Td structural transformations. For both 1H and 1Td phases without strain, Re-doped TMDCs have an n-type character and are non-magnetic, but the tensile strain could effectively induce and modulate the magnetism. Specifically, 1H-Re0.5Mo0.5S2 gets a maximum magnetic moment of 0.69 μB at a 6% uniaxial tensile strain along the armchair direction; along the zigzag direction it exhibits a significant magnetic moment (0.49 μB) at a 2.04% uniaxial tensile strain but then exhibits no magnetism in the range of [5.10%, 7.14%]. By contrast, for 1Td-Re0.5Mo0.5S2 a critical uniaxial tensile strain along the zigzag direction reaches up to ∼9.18%, and a smaller uniaxial tensile strain (∼5.10%) along the zigzag direction is needed to induce the magnetism in 1Td-Re0.5M0.5Te2. The results reveal that the magnetism of Re-doped TMDCs could be effectively induced and modulated by the tensile strain, suggesting that strain engineering could have significant applications in doped TMDCs.

Water dissociation and association on mirror twin boundaries in two-dimensional MoSe2: insights from density functional theory calculations.

The adsorption and dissociation of water molecules on two-dimensional transition metal dichalcogenides (TMDs) is expected to be dominated by point defects, such as vacancies, and edges. At the same time, the role of grain boundaries, and particularly, mirror twinboundaries (MTBs), whose concentration in TMDs can be quite high, is not fully understood. Using density functional theory calculations, we investigate the interaction of water, hydroxyl groups, as well as oxygen and hydrogen molecules with MoSe2 monolayers when MTBs of various types are present. We show that the adsorption of all species on MTBs is energetically favorable as compared to that on the basal plane of pristine MoSe2, but the interaction with Se vacancies is stronger. We further assess the energetics of various surface chemical reactions involving oxygen and hydrogen atoms. Our results indicate that water dissociation on the basal plane should be dominated by vacancies even when MTBs are present, but they facilitate water clustering through hydroxyl groups at MTBs, which can anchor water molecules and give rise to the decoration of MTBs with water clusters. Also, the presence of MTBs affects oxygen reduction reaction (ORR) on the MoSe2 monolayer. Unlike Se vacancies which inhibit ORR due to a high overpotential, it is found that the ORR process on MTBs is more efficient, indicating their important role in the catalytic activity of MoSe2 monolayer and likely other TMDs.

Data-driven assessment of chemical vapor deposition grown MoS2 monolayer thin films

Growth of high quality two-dimensional transition metal dichalcogenide monolayers with the desired microstructure and morphology is critical for enabling key technological solutions. This is a non-trivial problem because the processing space is vast and lack of a priori guidelines impedes rapid progress. A machine learning approach is discussed that leverages the data present in published growth experiments to predict growth performance in regions of unexplored parameter space. Starting from the literature data on MoS2 thin films grown using chemical vapor deposition (CVD), a database is manually constructed. Unsupervised and supervised machine learning methods are used to learn from the compiled data by extracting trends that underlie the formation of MoS2 monolayers. Design rules are uncovered that establish the phase boundaries classifying monolayers from other possible outcomes, which offers future guidance of CVD experiments.