Monolayer Molybdenum Disulfide Research Articles

Tunable Photoluminescence from Monolayer Molybdenum Disulfide

AbstractMonolayer molybdenum disulfide (1L MoS2), a promising optoelectronic material, emits strong visible photoluminescence (PL). Systematic control of the intensity, energy, and spectral width of PL from 1L MoS2 on silicon dioxide/silicon (SiO2/Si) is demonstrated via simple external treatments. Treating MoS2 with solutions formed from the superacid bis‐(trifluoromethanesulfonyl)amide (TFSA) enhances, blueshifts, and sharpens the PL. Treatments with solutions from structurally analogous chemicals that lack sulfur, in the case of bis(trifluoroacetamide) (BTFA), or lack fluorine, in the case of methanesulfonamide (MSA), show the same trend, suggesting a two‐component mechanism for TFSA involving the presence of electronegative species and sulfur vacancy passivation. Up to ≈100× enhancement of the PL intensity is achieved, with the peak blueshifted by ≈30 meV and the spectral linewidth halved. Conversely, direct thermal atomic layer deposition (ALD) of aluminum oxide (Al2O3) or hafnium oxide (HfO2) is found to suppress the PL by up to a factor of ≈3, redshift by up to ≈70 meV, and broaden by ≈3×. Single‐spot and mapping Raman/PL techniques are combined in a robust characterization process to associate changes in the PL character to charge doping. This work demonstrates the convenient tunability of the optical behavior of 1L MoS2 by varying the electron density.

Tunable Photoluminescence from Monolayer Molybdenum Disulfide

Tunable Photoluminescence from Monolayer Molybdenum Disulfide

Formation of oxygen protective layer on monolayer MoS2 via low energy electron irradiation.

Monolayer molybdenum disulfide (MoS2) semiconductors are the new generation of two-dimensional materials that possess several advantages compared to graphene due to their tunable bandgap and high electron mobility. Several approaches have been used to modify their physical properties for optical device applications. Here, we report a facile and non-destructive surface modification method for monolayer MoS2 via electron irradiation at a low, 5 kV accelerating voltage. After electron irradiation, the results of Raman and photoluminescence spectroscopy confirmed that the structure remains unchanged. However, when the modified surface was illuminated with a 532 nm laser for a prolonged period, the PL intensity was quenched as a result of oxygen desorption. Interestingly, the PL intensity can be recovered when left in ambient conditions for 10 h. The analysis of the PL spectrum revealed a decrease of trion, which is consistent with the readsorbed O2 molecules on the surface that deplete electrons and lead to PL recovery. We attribute this effect to the enhancement of the n-type character of monolayer MoS2 after electron irradiation. The sensitive nature of the modified surface to oxygen suggests that this approach may be used as a tool for the fabrication of MoS2 oxygen sensors.

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Research on two-dimensional material-based phototransistors has recently become a topic of great interest. However, the high number of design features, which impact the performance of these devices, and the multi-physical nature of the device operation make the accurate analysis of these devices a challenge. Here, we present a simple yet effective numerical framework to overcome this challenge. The one-dimensional framework is constructed on the drift-diffusion equations, Poisson’s equation, and wave propagation in multi-layered medium formalism. We apply this framework to study phototransistors made from monolayer molybdenum disulfide (MoS2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\hbox {MoS}}_{2}$$\\end{document}) placed on top of a back-gated silicon-oxide-coated silicon substrate. Numerical results, which show good agreement with the experimental results found in the literature, emphasize the necessity of including the inhomogeneous background for accurately calculating device metrics such as quantum efficiency and bandwidth. For the first time in literature, we calculate the phase noise of these phototransistors, which is a crucial performance metric for many applications where precise timing and synchronization are critical. We determine that applying a low drain-to-source voltage is the key requirement for low phase noise.

A Crayfish-Inspired Sensor Fusion Platform for Super Additive Integration of Visual, Chemical, and Tactile Information.

The concept of cross-sensor modulation, wherein one sensor modality can influence another's response, is often overlooked in traditional sensor fusion architectures, leading to missed opportunities for enhancing data accuracy and robustness. In contrast, biological systems, such as aquatic animals like crayfish, demonstrate superior sensor fusion through multisensory integration. These organisms adeptly integrate visual, tactile, and chemical cues to perform tasks such as evading predators and locating prey. Drawing inspiration from this, we propose a neuromorphic platform that integrates graphene-based chemitransistors, monolayer molybdenum disulfide (MoS2) based photosensitive memtransistors, and triboelectric tactile sensors to achieve "Super-Additive" responses to weak chemical, visual, and tactile cues and demonstrate contextual response modulation, also referred to as the "Inverse Effectiveness Effect." We hold the view that integrating bio-inspired sensor fusion principles across various modalities holds promise for a wide range of applications.

Electronic and optical properties of S vacancy and Br and I doped monolayer MoS2: A first-principle study

This study investigated the energy band structure (BS), electronic state density, and optical properties of monolayer molybdenum disulfide (ML-MoS2) with undoped, sulfur vacancy (VS), bromine (Br), and iodine (I) doped MoS2 systems using the first-principle approach based on density functional theory (DFT). Our results show that compared to undoped MoS2 system, Br, and I doped MoS2 systems induced lattice distortions. In addition, and the bandgap widths was reduced in VS, Br, and I doped systems, thereby effectively suppressing the compounding of electron–hole pairs. Moreover, the recombination rate of electron–hole pairs was reduced, which in turn increased the mobility of electrons transferred from the valence band (VB) to the conduction band (CB). Moreover, the VS and Br doped systems exhibited superior optical properties compared to undoped MoS2 system. Notably, the VS system exhibited the best optical properties, thereby demonstrating the strongest polarization capability. Our findings pave the way for realizing electronic devices and photocatalytic materials on MoS2 nanostructures.

Tuning the Electronic Characteristics of Monolayer MoS2‐Based Transistors by Ion Irradiation: The Role of the Substrate

AbstractThis study explores defect engineering in 2D materials using ion beam irradiation to modify the electrical and optical properties with potential in advancing quantum electronics and photonics. Helium and neon ions ranging from 5 to 7.5 keV are employed to manipulate charge transport in monolayer molybdenum disulfide (MoS2). In situ electrical characterization occurs without vacuum breakage post‐irradiation. Raman and photoluminescence spectroscopy quantify ion irradiation's impact on MoS2. Small doses of helium ion irradiation enhance monolayer MoS2 conductivity in field‐effect transistor geometry by inducing doping and substrate charging. Findings reveal a strong correlation between the electrical properties of MoS2 and the primary ion used, as well as the substrate on which the irradiation occurred. Using hexagonal boron nitride (h‐BN) as a buffer layer between MoS2 flake and SiO2 substrate yields distinct alterations in electrical behavior subsequent to ion irradiation compared to the MoS2 layer directly interfacing with SiO2. Molecular dynamics simulations and density functional theory provide insight into experimental results, emphasizing substrate influence on measured electrical properties post‐ion irradiation.

Ab Initio Modeling of Mixed-Dimensional Heterostructures: A Path Forward.

Understanding the electronic structure of mixed-dimensional heterostructures is essential for maximizing their application potential. However, accurately modeling such interfaces is challenging due to the complex interplay between the subsystems. We employ a computational framework integrating first-principles methods, including GW, density functional theory (DFT), and the polarizable continuum model, to elucidate the electronic structure of mixed-dimensional heterojunctions formed by free-base phthalocyanines and monolayer molybdenum disulfide. We assess the impact of dielectric screening across various scenarios, from isolated molecules to organic films on a substrate-supported monolayer. Our findings show that while polarization effects cause significant renormalization of molecular energy levels, band energies and alignments in the most relevant setup can be accurately predicted through DFT simulations of the individual subsystems. Additionally, we analyze orbital hybridization, revealing potential pathways for interfacial charge transfer. This study offers new insights into hybrid inorganic/organic interfaces and provides a practical computational protocol suitable for scaled-up studies.

Eight In. Wafer-Scale Epitaxial Monolayer MoS2.

Large-scale, high-quality, and uniform monolayer molybdenum disulfide(MoS2) films are crucial for their applications in next-generation electronics and optoelectronics. Epitaxy is a mainstream technique for achieving high-quality MoS2 films and is demonstrated at a wafer scale up to 4-in. In this study, the epitaxial growth of 8-in. wafer-scale highly oriented monolayer MoS2 on sapphire is reported as with excellent spatial homogeneity, using a specially designed vertical chemical vapor deposition (VCVD) system. Field effect transistors (FETs) based on the as-grown 8-in. wafer-scale monolayer MoS2 film are fabricated and exhibit high performances, with an average mobility and an on/off ratio of 53.5 cm2 V-1 s-1 and 107, respectively. In addition, batch fabrication of logic devices and 11-stage ring oscillators are also demonstrated, showcasing excellent electrical functions. This work may pave the way of MoS2 in practical industry-scale applications.

Modeling the coverage of MoS2 and WS2 thin films using in-situ spectroscopic ellipsometry

In-situ spectroscopic ellipsometry (SE) was used to analyze monolayer and few-layer samples of molybdenum disulfide (MoS2) and tungsten disulfide (WS2) grown by metalorganic chemical vapor deposition (MOCVD) on sapphire substrates. MoS2 and WS2 film growth times ranged from 5 – 40 min to achieve a range of film coalescence and surface coverage from less than a monolayer to considerable bilayer and additional layers. Post-growth measurements using atomic force microscopy, photoluminescence and Raman spectroscopy were used to assess the evolution of surface morphology and film properties with growth time to determine the areal coverage of monolayer, bilayer, multilayer and void regions. The room temperature SE spectra were modeled using an effective medium approximation to obtain the monolayer and bilayer dielectric functions of MoS2 and WS2. Using these distinct dielectric functions, changes in ellipsometry parameters associated with partial to full coverage of monolayers and bilayers were simulated. Such simulations will enable improved control of the layer-by-layer deposition of MoS2 and WS2 by monitoring in-situ spectroscopic ellipsometry.

Thickness-dependent electronic relaxation dynamics in solution-phase redox-exfoliated MoS2 heterostructures.

Electronic relaxation dynamics of solution-phase redox-exfoliated molybdenum disulfide (MoS2) monolayer and multilayer ensembles are described. MoS2 was exfoliated using polyoxometalate (POM) reductants. This process yields a colloidal heterostructure consisting of MoS2 2D sheet multilayers with surface-bound POM complexes. Using two-dimensional electronic spectroscopy, transient bleaching and photoinduced absorption signals were detected at excitation/detection energies of 1.82/1.87 and 1.82/1.80eV, respectively. Approximate 100-fs bandgap renormalization (BGR) and subsequent defect- and phonon-mediated relaxation on the picosecond timescale were resolved for several MoS2 thicknesses spanning from 1 to 2 L to ∼20 L. BGR rates were independent of sample thickness and slightly slower than observations for chemical vapor deposition-grown MoS2 monolayers. However, defect-mediated relaxation accelerated ∼10-fold with increased sample thicknesses. The relaxation rates increased from 0.33 ± 0.05 to 1.2 ± 0.1 and 3.1 ± 0.4ps-1 for 1-2 L, 3-4 L, and 20 L fractions. The thicknesses-dependent relaxation rates for POM-MoS2 heterostructures were modeled using a saturating exponential function that showed saturation at thirteen MoS2 layers. The results suggest that the increased POM surface coverage leads to larger defect density in the POM-MoS2 heterostructure. These are the first descriptions of the influence of sample thickness on electronic relaxation rates in solution-phase redox-exfoliated POM-MoS2 heterostructures. Outcomes of this work are expected to impact the development of solution-phase exfoliation of 2D metal-chalcogenide heterostructures.

One-Dimensional MoS2 Nanoscrolls as Miniaturized Memories.

Dimensionality of materials is closely related to their physical properties. For two-dimensional (2D) semiconductors such as monolayer molybdenum disulfide (MoS2), converting them from 2D nanosheets to one-dimensional (1D) nanoscrolls could contribute to remarkable electronic and optoelectronic properties, yet the rolling-up process still lacks sufficient controllability, which limits the development of their device applications. Herein we report a modified solvent evaporation-induced rolling process that halts at intermediate states and achieve MoS2 nanoscrolls with high yield and decent axial uniformity. The accordingly fabricated nanoscroll memories exhibit an on/off ratio of ∼104 and a retention time exceeding 103 s and can realize multilevel storage with pulsed gate voltages. Such open-end, high-curvature, and hollow 1D nanostructures provide new possibilities to manipulate the hysteresis windows and, consequently, the charge storage characteristics of nanoscale field-effect transistors, thereby holding great promise for the development of miniaturized memories.

Dielectric metasurface evolution from bulk to monolayer by strong coupling of quasi-BICs for second harmonic boosting

2D materials are promising candidates as nonlinear optical components for on-chip devices due to their ultrathin structure. In general, their nonlinear optical responses are inherently weak due to the short interaction thickness with light. Recently, there has been great interest in using quasi-bound states in the continuum (q-BICs) of dielectric metasurfaces, which are able to achieve remarkable optical near-field enhancement for elevating the second harmonic generation (SHG) emission from 2D materials. However, most studies focus on the design of combining bulk dielectric metasurfaces with unpatterned 2D materials, which suffer considerable radiation loss and limit near-field enhancement by high-quality q-BIC resonances. Here, we investigate the dielectric metasurface evolution from bulk silicon to monolayer molybdenum disulfide (MoS2), and discover the critical role of meta-atom thickness design on enhancing near-field effects of two q-BIC modes. We further introduce the strong-coupling of the two q-BIC modes by oblique incidence manipulation, and enhance the localized optical field on monolayer MoS2 dramatically. In the ultraviolet and visible regions, the MoS2 SHG enhancement factor of our design is 105 times higher than that of conventional bulk metasurfaces, leading to an extremely high nonlinear conversion efficiency of 5.8%. Our research will provide an important theoretical guide for the design of high-performance nonlinear devices based on 2D materials.

High-enhancement photoluminescence of monolayer MoS2 in hybrid plasmonic systems.

Monolayer molybdenum disulfide (M o S 2) has a weak light-matter interaction due to ultrathin thickness, which limits its potential application in lasing action. In this study, we propose a hybrid structure consisting of a nanocavity and Au nanoparticles to enhance the photon emission efficiency of monolayer M o S 2. Numerical simulations show that photoluminescence (PL) emission is significantly enhanced by introducing localized surface plasmon resonance (LSPR) to the proposed structure. Furthermore, an exciton energy band system is proposed to elucidate the physical mechanism of the PL process. By optimizing the spacer thickness, a high Purcell enhancement factor of 95 can be achieved. The results provided by this work pave the way to improve the PL efficiency of two-dimensional (2D) material, which constitutes a significant step towards the development of nanodevices such as nanolasers and sensors.

Interactions of monolayer molybdenum disulfide sheets with metalloid antimony in aquatic environment: Adsorption, transformation, and joint toxicity

The tremendous application potentiality of transitional metal dichalcogenides (TMDs), such as molybdenum disulfide (MoS2) nanosheets, will unavoidably lead to increasing release into the environment, which could influence the fate and toxicity of co-existed contaminants. The present study discovered that 59.8 % of trivalent antimony [Sb(III)] was transformed by MoS2 to pentavalent Sb [Sb(V)] in aqueous solutions under light illumination, which was due to hole oxidation on the nanosheet surfaces. A synergistic toxicity between MoS2 and Sb(III, V) to algae (Chlorella vulgaris) was observed, as demonstrated by the lower median-effect concentrations of MoS2 + Sb(III)/Sb(V) (13.1 and 20.9 mg/L, respectively) than Sb(III)/Sb(V) (38.8 and 92.5 mg/L, respectively) alone. Particularly, MoS2 at noncytotoxic doses notably increased the bioaccumulation of Sb(III, V) in algae, causing aggravated oxidative damage, photosynthetic inhibition, and structural alterations. Metabolomics indicated that oxidative stress and membrane permeabilization were primarily associated with down-regulated amino acids involved in glutathione biosynthesis and unsaturated fatty acids. MoS2 co-exposure remarkably decreased the levels of thiol antidotes (glutathione and phytochelatins) and aggravated the inhibition on energy metabolism and ATP synthesis, compromising the Sb(III, V) detoxification and efflux. Additionally, extracellular P was captured by the nanosheets, also contributing to the uptake of Sb(V). Our findings emphasized the nonignorability of TMDs even at environmental levels in affecting the ecological hazard of metalloids, providing insight into comprehensive safety assessment of TMDs.

Wafer-Scale epitaxial molybdenum disulfide ultrathin film on sapphire prepared by low-energy reactive magnetron sputtering

Molybdenum disulfide, a two-dimensional semiconductor, has found broad applications in various functional devices. Currently, developing a reliable method for growing wafer-scale monolayer molybdenum disulfide presents a significant challenge in its integration into the contemporary semiconductor industry. This study employed low-energy reactive magnetron sputtering with hydrogen disulfide gas to deposit wafer-scale epitaxial few-layer and monolayer molybdenum disulfide on c-sapphire substrates. The epitaxial molybdenum disulfide nano-thin film was examined using scanning nano-probe X-ray diffraction technique, revealing a single grain size of no less than 50 × 50 μm2. Furthermore, the growth of monolayer molybdenum disulfide on both c-sapphire and thermal silicon oxide substrates was verified through Raman microscope. Measurements of photoluminescence and X-ray photoelectron spectroscopy also confirmed the monolayer state of the sputtered nano-thin films. This study suggests that reactive magnetron sputtering with hydrogen disulfide gas offers a cost-effective, scalable method for growing large-area molybdenum disulfide nano-thin films, thereby holding significant potential for practical semiconductor industrial applications.

A 2D Cryptographic Hash Function Incorporating Homomorphic Encryption for Secure Digital Signatures.

User authentication is a critical aspect of any information exchange systemwhich verifies the identities of individuals seeking access to sensitive information. Conventionally, this approachrelies on establishing robust digital signature protocolswhich employ asymmetric encryption techniques involving a key pair consisting of a public key and its matching private key. In this article, a user verification platform constructed using integrated circuits (ICs) with atomically thin two-dimensional (2D) monolayer molybdenum disulfide (MoS2 ) memtransistors is presented. First, generation of secure cryptographic keys is demonstrated by exploiting the inherent stochasticity of carrier trapping and detrapping at the 2D/oxide interface trap sites. Subsequently, the ability to manipulate the functionality of logical NOR is leveraged to create a secure one-way hash function which when homomorphically operated upon with NAND, XOR, OR, NOT, and AND logic circuits generate distinct digital signatures. These signatures when subsequently decrypted, verify the authenticity of the receiver while ensuring complete preservation of data integrity and confidentiality as the underlying information is never revealed. Finally, the advantages of implementing a NOR-based hashing techniques in comparison to the conventional XOR-based encryption method are established. This demonstration highlights the potential of 2D-based ICs in developing critical hardware information security primitives.

Epitaxy of wafer-scale single-crystal MoS2 monolayer via buffer layer control

Monolayer molybdenum disulfide (MoS2), an emergent two-dimensional (2D) semiconductor, holds great promise for transcending the fundamental limits of silicon electronics and continue the downscaling of field-effect transistors. To realize its full potential and high-end applications, controlled synthesis of wafer-scale monolayer MoS2 single crystals on general commercial substrates is highly desired yet challenging. Here, we demonstrate the successful epitaxial growth of 2-inch single-crystal MoS2 monolayers on industry-compatible substrates of c-plane sapphire by engineering the formation of a specific interfacial reconstructed layer through the S/MoO3 precursor ratio control. The unidirectional alignment and seamless stitching of MoS2 domains across the entire wafer are demonstrated through cross-dimensional characterizations ranging from atomic- to centimeter-scale. The epitaxial monolayer MoS2 single crystal shows good wafer-scale uniformity and state-of-the-art quality, as evidenced from the ~100% phonon circular dichroism, exciton valley polarization of ~70%, room-temperature mobility of ~140 cm2v−1s−1, and on/off ratio of ~109. Our work provides a simple strategy to produce wafer-scale single-crystal 2D semiconductors on commercial insulator substrates, paving the way towards the further extension of Moore’s law and industrial applications of 2D electronic circuits.

The Origin of Threshold Reduction in Random Lasers Based on MoS2/Au NPs: Charge Transfer

Random lasers have attracted much attention in recent years owing to their advantages of a simple fabrication process, low processing cost, and material flexibility for any lasing wavelengths. They provide a roadmap for the design of ultra-bright lighting, displays, etc. However, the threshold reduction in random nanolasers remains a challenge in practical applications. In this work, lower-threshold random laser action from monolayer molybdenum disulfide film-encapsulated Au nanoparticles (MoS2/Au NPs) is demonstrated. The observed laser action of the MoS2/Au NPs shows a lower threshold of about 0.564 µJ/mm2, which is about 46.2% lower than the threshold of random lasers based on Au NPs. We proposed that the charge transfer between MoS2 and the gain material is the main reason for the reduction in the random laser threshold. The finite-difference time-domain (FDTD) method was used to calculate the lasing action of these two nanostructures. When charge transfer is taken into account, the theoretically calculated threshold of the MoS2/Au NPs is reduced by 46.8% compared to Au NP samples, which is consistent with the experimental results. This study provides a new mechanism to achieve low-threshold and high-quality random lasers, which has the potential to facilitate the application of random lasers and the development of high-performance optoelectronic devices.

Symmetry Breaking and Spin-Orbit Coupling for Individual Vacancy-Induced In-Gap States in MoS2 Monolayers.

Spins confined to point defects in atomically thin semiconductors constitute well-defined atomic-scale quantum systems that are being explored as single-photon emitters and spin qubits. Here, we investigate the in-gap electronic structure of individual sulfur vacancies in molybdenum disulfide (MoS2) monolayers using resonant tunneling scanning probe spectroscopy in the Coulomb blockade regime. Spectroscopic mapping of defect wave functions reveals an interplay of local symmetry breaking by a charge-state-dependent Jahn-Teller lattice distortion that, when combined with strong (≃100 meV) spin-orbit coupling, leads to a locking of an unpaired spin-1/2 magnetic moment to the lattice at low temperature, susceptible to lattice strain. Our results provide new insights into the spin and electronic structure of vacancy-induced in-gap states toward their application as electrically and optically addressable quantum systems.