Properties Of Transition Metal Dichalcogenides Research Articles

Efficient detection of lung cancer biomarkers using functionalized transition metal dichalcogenides (MoS2) Monolayers: DFT study

Selective sensing properties of transition metal dichalcogenides (MoX2, X = S, Se) towards specific volatile organic compounds (VOCs) associated with lung-cancer are investigated using state-of-the-art density-functional theory (DFT) methods. In the present investigation, a combination of DFT and the non-equilibrium Green’s functions (NEGF) formalism are employed to probe the sensing of four VOCs; namely: (i) Isoprene “C5H8”, (ii) Toluene “C7H8”, (iii) Cyclopropanone “C3H4O”, and (iv) Isopropanol “C3H8O”; and four interfering air molecules CO2, H2O, N2 and O2. We find that the doping of single atom of selected transition metals (TMs = Mn, Fe, Ni, Cu) can enhance both the sensitivity and the selectivity of MoX2. Our results show that the selectivity is rather distinct towards the detection of VOCs when TMs doping is targeting the chalcogenide site. Adsorption energies, charge transfers, electronic properties through density of states and band structures, and the sensor responses are obtained in all the cases, particularly for C5H8 and C3H8O, which show superior selectivities. Enhanced selectivity is attributed to the enhancement in the polarity of the substrate after the TMs doping targeting the chalcogenide sites. Our work demonstrates the potential of MoX2 based single atom catalysts as efficient biosensor towards the specific VOCs for the early diagnosis of lung cancer.PACS Numbers: 31.15.E-, 68.43.-h, 68.43.Fg, 82.33.Pt, 87.15.Aa, 87.15.Kg, 87.19.Xx, 87.19.xj.

Experimental Investigation of Superconductivity in PdSSe Under High Pressure

AbstractAnalysis of the superconducting properties of transition metal dichalcogenides (TMDs) under high pressures offers valuable insights to guide the design and synthesis of high‐performance superconducting materials. Herein, the effect of pressure is investigated on the superconductivity of a typical van der Waals layered TMDs material, PdSSe, by measuring its transport properties. After initially increased pressure, superconductivity emerges at 10.2 GPa, with a critical superconducting temperature (Tc) of ≈5.1 K, accompanied by the diminishing charge density wave (CDW) that is originally strengthening. Then, the Tc gradually increases with increasing pressure, reaching 12.1 K at the maximum pressure. The study provides experimental evidence for the superconductivity of PdSSe, and to the best of the knowledge, this is the first report on the observation of amplified CDW phenomena under increasing pressure in nonmagnetic TMDs. The abnormal enhancement of CDW transition temperature at low pressure is consistent with the upward trend of resistance, which is related to the electron–electron interaction. Moreover, synchrotron X‐ray diffraction experiments reveal two additional structural phase transitions.

Atomic insight into the effects of precursor clusters on monolayer WSe2.

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been attracting much attention due to their rich physical and chemical properties. At the end of the chemical vapor deposition growth of 2D TMDCs, the adsorption of excess precursor clusters onto the sample is unavoidable, which will have significant effects on the properties of TMDCs. This is a concern to the academic community. However, the structures of the supported precursor clusters and their effects on the properties of the prepared 2D TMDCs are still poorly understood. Herein, taking monolayer WSe2 as the prototype, we investigated the structure and electronic properties of SeN, WN (N = 1-8), and W8-NSeN (N = 1-7) clusters adsorbed on monolayer WSe2 to gain atomic insight into the precursor cluster adsorption. In contrast to W clusters that tightly bind to the WSe2 surface, Se clusters except for Se1 and Se2 are weakly adsorbed onto WSe2. The interaction between W8-NSeN (N = 1-7) clusters and the WSe2 monolayer decreases with the increase in the Se/W ratio and eventually becomes van der Waals interaction for W1Se7. According to the phase diagram, increasing the Se/W ratio by changing the experimental conditions will increase the ratio of SeN and W1Se7 clusters in the precursor, which can be removed by proper annealing after growth. W clusters induce lots of defect energy levels in the band gap region, while the adsorption of W1Se7 and SeN clusters (N = 3-6, 8) promotes the spatial separation of photo generated carriers at the interface, which is important for optoelectronic applications. Our results indicate that by controlling the Se/W ratio, the interaction between the precursor clusters and WSe2 as well as the electronic properties of the prepared WSe2 monolayer can be effectively tuned, which is significant for the high-quality growth and applications of WSe2.

Adhesion properties of MoS<sub>2</sub>/SiO<sub>2 </sub>interface: Size and temperature effects

The interface adhesion properties are crucial for designing and fabricating two-dimensional materials and related nanoelectronic and nanomechanical devices. Although some progress of the interface adhesion properties of two-dimensional materials has been made, the underlying mechanism behind the size and temperature dependence of interface adhesion energy and related physical properties from the perspective of atomistic origin remain unclear. In this work, we investigate the effects of size and temperature on the thermal expansion coefficient and Young’s modulus of MoS<sub>2</sub> as well as interface adhesion energy of MoS<sub>2</sub>/SiO<sub>2</sub> based on the atomic-bond-relaxation approach and continuum medium mechanics. It is found that the thermal expansion coefficient of monolayer MoS<sub>2</sub> is significantly larger than that of its few-layer and bulk counterparts under the condition of ambient temperature due to size effect and its influence on Debye temperature, whereas the thermal expansion coefficient increases with temperature going up and almost tends to a constant as the temperature approaches the Debye temperature. Moreover, the variations of bond identity induced by size effect and temperature effect will change the mechanical properties of MoS<sub>2</sub>. When the temperature is fixed, the Young’s modulus of MoS<sub>2</sub> increases with size decreasing. However, the thermal strain induces the volume expansion, resulting in the Young’s modulus of MoS<sub>2</sub> decreasing. Furthermore, the size and temperature dependence of lattice strain, mismatch strain of interface, and Young’s modulus will lead the van der Waals interaction energy and elastic strain energy to change, resulting in the change of interface adhesion energy of MoS<sub>2</sub>/SiO<sub>2</sub>. Noticeably, the interface adhesion energy of MoS<sub>2</sub>/SiO<sub>2</sub> gradually increases with MoS<sub>2</sub> size decreasing, while the thermal strain induced by temperature causes interface adhesion energy of MoS<sub>2</sub>/SiO<sub>2</sub> to decrease with temperature increasing. In addition, we predict the conditions of the interface separation of MoS<sub>2</sub>/SiO<sub>2</sub> under different sizes and temperatures. Our results demonstrate that increasing both size and temperature can significantly reduce the interface adhesion energy, which is of great benefit in detaching MoS<sub>2</sub> film from the substrate. Therefore, the proposed theory not only clarifies the physical mechanism regarding the interface adhesion properties of transition metal dichalcogenides (TMDs) membranes, but also provides an effective way to design TMDs-based nanodevices for desirable applications.

Mitigating substrate effects of the van der Waals semiconductors using perfluoropolyether self-assembled monolayers

The properties of transition metal dichalcogenides (TMDCs) are critically dependent on the dielectric constant of the substrate, which is a significant obstacle to their application. To address this issue, we...

Discovering a Wigner-like crystal and soft x-ray correlated plasmons and their couplings in a transition metal dichalcogenide

Low-dimensional systems host many exotic physical properties. Using extended resonant soft x-ray scattering supported with theoretical calculations, we observe concomitantly a Wigner-like crystal in a stripe-like QHKL = (001) superlattice with surprisingly long coherence lengths and new soft x-ray correlated plasmons in WS2. A new electronic transition is found at 125 K upon cooling, which is a transition from two-dimensional ordering to three-dimensional ordering, a result of p–d hybridization anisotropy and electronic correlations. Our result shows the importance of the interplay of long-range electron–electron correlation and short-range electronic screening in determining electronics and optical properties of transition metal dichalcogenides.

Optical Enhancement of Indirect Bandgap 2D Transition Metal Dichalcogenides for Multi-Functional Optoelectronic Sensors.

The unique electrical and optical properties of transition metal dichalcogenides (TMDs) make them attractive nanomaterials for optoelectronic applications, especially optical sensors. However, the optical characteristics of these materials are dependent on the number of layers. Monolayer TMDs have a direct bandgap that provides higher photoresponsivity compared to multilayer TMDs with an indirect bandgap. Nevertheless, multilayer TMDs are more appropriate for various photodetection applications due to their high carrier density, broad spectral response from UV to near-infrared, and ease of large-scale synthesis. Therefore, this review focuses on the modification of the optical properties of devices based on indirect bandgap TMDs and their emerging applications. Several successful developments in optical devices are examined, including band structure engineering, device structure optimization, and heterostructures. Furthermore, it introduces cutting-edge techniques and future directions for optoelectronic devices based on multilayer TMDs.

Ultrafast Electronic Relaxation Dynamics of Atomically Thin MoS2 Is Accelerated by Wrinkling.

Strain engineering is an attractive approach for tuning the local optoelectronic properties of transition metal dichalcogenides (TMDs). While strain has been shown to affect the nanosecond carrier recombination dynamics of TMDs, its influence on the sub-picosecond electronic relaxation dynamics is still unexplored. Here, we employ a combination of time-resolved photoemission electron microscopy (TR-PEEM) and nonadiabatic ab initio molecular dynamics (NAMD) to investigate the ultrafast dynamics of wrinkled multilayer (ML) MoS2 comprising 17 layers. Following 2.41 eV photoexcitation, electronic relaxation at the Γ valley occurs with a time constant of 97 ± 2 fs for wrinkled ML-MoS2 and 120 ± 2 fs for flat ML-MoS2. NAMD shows that wrinkling permits larger amplitude motions of MoS2 layers, relaxes electron-phonon coupling selection rules, perturbs chemical bonding, and increases the electronic density of states. As a result, the nonadiabatic coupling grows and electronic relaxation becomes faster compared to flat ML-MoS2. Our study suggests that the sub-picosecond electronic relaxation dynamics of TMDs is amenable to strain engineering and that applications which require long-lived hot carriers, such as hot-electron-driven light harvesting and photocatalysis, should employ wrinkle-free TMDs.

Controllable Synthesis of 2H-1T' Mox Re(1- x ) S2 Lateral Heterostructures and Their Tunable Optoelectronic Properties.

Constructing heterostructures and doping are valid ways to improve the optoelectronic properties of transition metal dichalcogenides (TMDs) and optimize the performance of TMDs-based photodetectors. Compared with transfer techniques, chemical vapor deposition (CVD) has higher efficiency in preparing heterostructures. As for the one-step CVD growth of heterostructures, cross-contamination between the two materials may occur during the growth process, which may provide the possibility of one-step simultaneous realization of controllable doping and formation of alloy-based heterostructures by finely tuning the growth dynamics. Here, 2H-1T' Mox Re(1- x ) S2 alloy-to-alloy lateral heterostructures are synthesized through this one-step CVD growth method, utilizing the cross-contamination and different growth temperatures of the two alloys. Due to the doping of a small amount of Re atoms in 2H MoS2 , 2H Mox Re(1- x ) S2 has a high response rejection ratio in the solar-blind ultraviolet (SBUV) region and exhibits a positive photoconductive (PPC) effect. While the 1T' Mox Re(1- x ) S2 formed by heavily doping Mo atoms into 1T' ReS2 will produce a negative photoconductivity (NPC) effect under ultraviolet (UV) laser irradiation. The optoelectronic property of 2H-1T' Mox Re(1- x ) S2 -based heterostructures can be modulated by gate voltage. These findings are expected to expand the functionality of traditional optoelectronic devices and have potential applications in optoelectronic logic devices. This article is protected by copyright. All rights reserved.

Data-driven study of magnetic anisotropy in transition metal dichalcogenide monolayers

We investigate the magnetic and thermodynamic properties of transition metal dichalcogenides of the form A2X4, based on monolayer Mn2Se4, using data analytics. In particular, we combine first-principles calculations with machine learning methods to elucidate the microscopic origins of the magnetocrystalline anisotropy in these materials. We explore a large number of candidate transition metal dichalcogenides by varying the chemical compositions of the transition metal (A) sites and the chalcogen (X) sites. We investigate the magnetocrystalline anisotropy by studying the transition between in-plane and out-of-plane magnetization. Using data analytics we demonstrate that the interplay between the spin–orbit interactions of the chalcogen and transition metal atoms can impact the magnetic behavior. Finally, we identity several novel transition metal dichalcogenides with large anisotropies that are chemically stable.

Photoelectric structure and magnetic changes caused by niobium disulfide adsorbing (non)-metal atoms under defects.

The property transition between metal and semiconductor is the key to improving the properties of transition metal dichalcogenides (TMDCs). The adsorption of the NbS2 compound in the defect state was adjusted for the first time. The hybrid system overwrites the original surface mechanism of NbS2 and induces indirect band gaps. This modulation mode makes NbS2 convert into a semiconductor and effectively improves the catalytic activity of the material in the system. In addition, the original local magnetic moment of the compound is concentrated in the vacancy region and is improved. The optical properties of the adsorption system indicate that NbS2 compounds can be effectively applied in visible and low-frequency ultraviolet regions. This provides a new idea for the design of the NbS2 compound as a two-dimensional photoelectric material. In the study, we assume that only one atom is adsorbed on the NbS2 supercell of the defect, and the distance between the two adjacent atoms exceeds 12.74 Å, so the interaction between atoms is ignored in the study. Adsorbed atoms include nonmetallic elements (H, B, C, N, O, F), metallic elements (Fe, Co), and noble metal elements (Pt, Au, Ag). The density functional theory (DFT) was used in the experiment. The non-conservative pseudopotential method was used in the calculation to optimize the crystal structure geometrically. The approximate functional is Heyd-Scuseria-Ernzerhof (HSE06). The calculation method includes the spin-orbit coupling (SOC) effect. The crystal relaxation optimization uses a 7 × 7 × 1 k point grid to calculate niobium disulfide's photoelectric and magnetic properties. A vacuum space of 15Å is introduced in the direction outside the plane, and the free boundary condition is adopted to avoid the interaction between atomic layers. For the convergence parameter setting, the interatomic force of all composite systems is less than 0.03 eV/Å, and the lattice stress is less than 0.05 Gpa.

Optical signatures of suppressed carrier localization in encapsulated WSe2 monolayer

Low carrier mobility, closely associated with the formation of localized states, is the major bottleneck of utilizing the unique quantum transport properties in transition metal dichalcogenides (TMDCs). Here, we demonstrate an effective method to quantify the localization energy based on the temperature-dependent spectral variation of photoluminescence (PL) in pristine and hexagonal boron nitride (h-BN) encapsulated monolayer (ML) WSe2. Considering the protecting capability of h-BN against contamination and degradation, while not affecting the electronic structure as an insulating dielectric, the localization energy was comparatively extracted out of PL spectra in pristine and encapsulated ML WSe2. In pristine ML WSe2, two distinctive energy traces were resolved with an energy difference of about 17 meV, which was associated with the localized state revealed below 200 K. Clear evidence for the carrier localization was also evident in the integrated PL intensity trace with temperature as the trace from pristine ML clearly deviates from the dark-exciton-like behavior of ML WSe2, violating the spin selection rule of the lowest exciton state. In clear contrast, the temperature dependency of the h-BN encapsulated ML WSe2 in PL spectra matches well with the typical Varshni formula of free excitonic peaks and the integrated intensity trace of thermally populated spin subbands. Our study suggests that the h-BN encapsulation could suppress the carrier localization channels by avoiding surface oxidation due to air exposure and could provide insights into how one could preserve the excitonic features in TMDC materials and devices.

Signatures of Temperature-Driven Lifshitz Transition in Semimetal Hafnium Ditelluride

Temperature-driven change of Fermi surface has been attracting attention recently as it is fundamental and essential to understand a metallic system. We report the magnetotransport anomalies in the semimetal HfTe2 single crystals. The magnetoresistance behavior at high temperatures obeys Kohler’s rule which can lead to the field-induced resistivity upturn behavior as observed. When the temperature is decreased to around 30 K, Kohler’s rule becomes inapplicable, indicating the change of the Fermi surface in HfTe2. The Hall analyses and extended Kohler’s plot reveal abrupt change of carrier densities and mobilities near 30 K. These results suggest that the chemical potential may shift as the temperature increases and the shift causes an electron pocket to vanish. Our work of the temperature-driven Lifshitz transition in HfTe2 is relevant to understanding of the transport anomalies and exotic physical properties in transition-metal dichalcogenides.

Detection of Electron Paramagnetic Resonance Spectra of Optically Induced Carriers with the Properties of the Effective Mass in the WS2 Transition Metal Dichalcogenide

The spin properties of transition metal dichalcogenides are of interest for applications in spintronics. Anisotropic electron paramagnetic resonance spectra in a WS2 single crystal under optical excitation have been detected. These spectra assumingly belong to localized carriers near the valence band and reflect features of the 5d shell of the crystal. It has been shown that the g-factor for the magnetic field perpendicular to the c‑axis of the crystal (in-plane magnetic field) is larger than that for the magnetic field parallel to the c‑axis (perpendicular to the layer plane), which can provide information on the type of the 5d function. The discussed center is most likely described by the 5d({{z}^{2}} - {{r}^{2}}) wavefunction, which can be associated with the valence band of the crystal.

Macroscopic transition metal dichalcogenides monolayers with uniformly high optical quality

The unique optical properties of transition metal dichalcogenide (TMD) monolayers have attracted significant attention for both photonics applications and fundamental studies of low-dimensional systems. TMD monolayers of high optical quality, however, have been limited to micron-sized flakes produced by low-throughput and labour-intensive processes, whereas large-area films are often affected by surface defects and large inhomogeneity. Here we report a rapid and reliable method to synthesize macroscopic-scale TMD monolayers of uniform, high optical quality. Using 1-dodecanol encapsulation combined with gold-tape-assisted exfoliation, we obtain monolayers with lateral size > 1 mm, exhibiting exciton energy, linewidth, and quantum yield uniform over the whole area and close to those of high-quality micron-sized flakes. We tentatively associate the role of the two molecular encapsulating layers as isolating the TMD from the substrate and passivating the chalcogen vacancies, respectively. We demonstrate the utility of our encapsulated monolayers by scalable integration with an array of photonic crystal cavities, creating polariton arrays with enhanced light-matter coupling strength. This work provides a pathway to achieving high-quality two-dimensional materials over large areas, enabling research and technology development beyond individual micron-sized devices.

Boosting the sodium-ion storage capability of MoSe2 through the synergistic effect of rational sulfur substituting and carbon compositing

Molybdenum selenide (MoSe2) has been regarded as a promising anode for sodium-ion storage due to its large interlayer space, acceptable electronic conductivity, and considerable theoretical capacity, but suffers insufficient active sites and serious volume variation, leading to low reversible capacity and poor cycling lifespans. Herein, a facile one-pot hydrothermal method is developed to achieve sulfur substituting and carbon compositing simultaneously and employed to boost the sodium ion storage properties of MoSe2. The effects of sulfur substituting and carbon compositing on the redox kinetics and sodium-ion storage performance are investigated. In short, sulfur substitution mainly enhances the electronic/ionic conductivity and specific capacity of the MoSe2 by tailoring the electron structures and creating anionic vacancies. Carbon compositing mainly improves the cycling stability due to the alleviative aggregation of active materials and the prohibited active materials dissolution. As a result, the optimized MoSe2-xSx@C electrode presents 348.6 mAh g−1 at 0.1 A g−1, and can endure long-term cycling at 4 A g−1 after 600 cycles with acceptable capacity retention of 83.9%, much better than the pure MoSe2 electrode and the MoSe2-xSx electrodes. This work may provide a facile method to enhance the sodium ion storage properties of transition metal dichalcogenides.

Hot exciton effect in photoluminescence of monolayer transition metal dichalcogenide

AbstractHot excitons are usually neglected in optical spectroscopy in two‐dimensional semiconductors for the sake of momentum conservation, as the majority of hot excitons are out of light cones. In this letter, we elaborate on the contribution of hot excitons to optical properties of monolayer Molybdenum diselenide (MoSe2) with photoluminescence (PL) and PL excitation (PLE) spectroscopy. With the excitation‐intensity‐dependent PL, temperature‐dependent PL and PLE experiments combined with the simulations, we experimentally distinguish the influences of the exciton temperature and the lattice temperature in the PL spectrum. It is concluded that the acoustic phonon‐assisted PL accounts for the non‐Lorentzian high energy tail in the PL spectrum, and the hot exciton effect is significant to linear optical properties of transition metal dichalcogenides. Besides, the effective exciton temperature is found to be several tens of Kelvin higher than the lattice temperature at non‐resonant optical excitation. It indicates that the exciton temperature needs to be carefully taken into account when considering the exciton‐related quantum phase phenomena such as exciton condensation. It is experimentally demonstrated that the effective exciton temperature can be tuned by excitation energy.Key points The acoustic phonon‐assisted photoluminescence (PL) accounts for the non‐Lorentzian high‐energy tail in the PL spectrum. “Hot” excitons play a significant role in optical properties of two‐dimensional transition metal dichalcogenides. The effective exciton temperature could be tuned by excitation energy.

Direct Observation of Self-Hybridized Exciton-Polaritons and Their Valley Polarizations in a Bare WS2 Layer.

The strong excitonic properties of transition metal dichalcogenides (TMD) have led to the successful demonstration of exciton-polaritons (EPs) in various optical cavity structures. Recently, self-hybridized EPs have been discovered in a bare TMD layer, but experimental investigation is still lacking because of their nonradiative nature. Herein, the direct observation of self-hybridized EPs in a bare multilayer WS2 via the evanescent field coupling technique is reported. Because of the thickness-dependent Rabi splitting energy, the dispersion curves of the EPs change sensitively with sample thickness. Moreover, continuous tuning of EP dispersion curves is demonstrated by controlling the excitation laser power. Lastly, it is observed that guided EPs retain valley polarization up to 0.2 at room temperature, representing a valley-preserved strong coupling regime. It is believed that the high tunability and valley polarization properties of the guided EPs in bare TMD layers can facilitate new nanophotonic and valleytronic applications.

Transition Metal Dichalcogenides Interfacing Photoactive Molecular Components for Managing Energy Conversion Processes

The remarkable properties of transition metal dichalcogenides (TMDs), represented by molybdenum disulfide (MoS2), make them promising candidates as active nanomaterials for optoelectronics, electronic, and electrochemical applications. Different exfoliation methods can drastically alter the properties of TMDs, changing the metallic–semiconducting polytype or creating defects, while further chemical surface modification offers additional routes to tune the properties of TMDs by adding new functions. In this timely review, a general outlook on the most representative examples of TMD‐based materials interfacing photoactive components, such as porphyrins and phthalocyanines among others, yielding electron donor–acceptor hybrids and nanoensembles for energy conversion schemes, specifically for managing charge transfer events, is presented. The covalent and noncovalent approaches for the coupling of the aforesaid photoactive species with TMDs and their photophysical characterization are highlighted. Moreover, the properties, preparation methods, and characterization techniques of TMDs, mainly for MoS2, are also briefly discussed. Finally, perspectives and challenges of this emerging area are showcased, aiming to increase scientific attention and enhance not only the performance but also their applicability.

The non-volatile electrostatic doping effect in MoTe2 field-effect transistors controlled by hexagonal boron nitride and a metal gate

The electrical and optical properties of transition metal dichalcogenides (TMDs) can be effectively modulated by tuning their Fermi levels. To develop a carrier-selectable optoelectronic device, we investigated intrinsically p-type MoTe2, which can be changed to n-type by charging a hexagonal boron nitride (h-BN) substrate through the application of a writing voltage using a metal gate under deep ultraviolet light. The n-type part of MoTe2 can be obtained locally using the metal gate pattern, whereas the other parts remain p-type. Furthermore, we can control the transition rate to n-type by applying a different writing voltage (i.e., − 2 to − 10 V), where the n-type characteristics become saturated beyond a certain writing voltage. Thus, MoTe2 was electrostatically doped by a charged h-BN substrate, and it was found that a thicker h-BN substrate was more efficiently photocharged than a thinner one. We also fabricated a p–n diode using a 0.8 nm-thick MoTe2 flake on a 167 nm-thick h-BN substrate, which showed a high rectification ratio of ~ 10−4. Our observations pave the way for expanding the application of TMD-based FETs to diode rectification devices, along with optoelectronic applications.