Notable synthesis, properties and chemical gas sensing trends on molybdenum disulphides and diselenides two-dimensional nanostructures: A critical review.

Evaluation of synthesis methods, notable properties, and chemical gas sensing properties of molybdenum disulphides and diselenides two-dimensional nanosheets is unfold. This is motivated by the fact that the two dichalcogenides have good sensitivity and selectivity to different harmful gases at ambient temperatures. Synthesis methods explored include exceptional top-down and bottom-up approaches, which consider physical and chemical compositional inceptions. Mechanical exfoliation in both molybdenum disulphides and diselenides nanosheets demonstrate good crystalline purity with structural alterations under varying stacking conditions. These chalcogenides exhibit low energy band gaps of ±1.80 eV for MoS2 and ±1.60 eV for MoSe2, which reduces with introduction of impurities. Thus, upon doping with other metal elements, a transformation from either n-type or p-type semiconductors is normally observed, leading to tuneable electronic properties. Thus, different gases such as methane, ethanol, toluene, ammonia, nitrogen oxide have been systematically detected using molybdenum disulphide and diselenide based thin films as sensing platforms. This review highlights structural, electronic and morphological characteristics of the two dichalcogenides which influences the sensitivity and selectivity ability for a couple of gases at ambient temperatures. The strategies for enhancing the selectivity by introducing defects, impurities and interfacing with other composites expanding the choice of these gases wider is also discussed in details. The review also provides overviews of challenges and limitations that open new research avenues to further enriching both chalcogenides as flexible, stable and cost effective state-of-the-art chemical gas sensors.

Air stability of monolayer WSi2N4 in dark and bright conditions.

Two-dimensional materials with chemical formula MA2Z4 are a promising class of materials for optoelectronic applications. To exploit their potential, their stability with respect to air pollution has to be analyzed under different conditions. In a first-principle study based on density functional theory, we investigate the adsorption of three common environmental gas molecules (O2, H2O, and CO2) on monolayer WSi2N4, an established representative of the MA2Z4 family. The computed adsorption energies, charge transfer, and projected density of states of the polluted monolayer indicate a relatively weak interaction between substrate and molecules resulting in an ultrashort recovery time of the order of nanoseconds. O2 and water introduce localized states in the upper valence region but do not alter the semiconducting nature of WSi2N4 nor its band-gap size apart from a minor variation of a few tens of meV. Exploring the same scenario in the presence of photogenerated electrons and holes, we do not notice any substantial difference except for O2 chemisorption when negative charge carriers are in the system. In this case, monolayer WSi2N4 exhibits signs of irreversible oxidation, testified by an adsorption energy of -5.5 eV leading to an infinitely long recovery time, a rearrangement of the outermost atomic layer bonding with the pollutant, and n-doping of the system. Our results indicate stability of WSi2N4 against H2O and CO2 in both dark and bright conditions, suggesting the potential of this material in nanodevice applications.

Signature of pressure-induced topological phase transition in ZrTe5.

The layered van der Waals material ZrTe5 is known as a candidate topological insulator (TI), however its topological phase and the relation with other properties such as an apparent Dirac semimetallic state is still a subject of debate. We employ a semiclassical multicarrier transport (MCT) model to analyze the magnetotransport of ZrTe5 nanodevices at hydrostatic pressures up to 2 GPa. The temperature dependence of the MCT results between 10 and 300 K is assessed in the context of thermal activation, and we obtain the positions of conduction and valence band edges in the vicinity of the chemical potential. We find evidence of the closing and re-opening of the band gap with increasing pressure, which is consistent with a phase transition from weak to strong TI. This matches expectations from ab initio band structure calculations, as well as previous observations that CVT-grown ZrTe5 is a weak TI in ambient conditions.

Stacking-dependent structural and electronic properties of trilayer γ-graphyne: An approach for new 2D carbon allotropes.

Vertical stacks of two-dimensional (2D) materials with interlayer van der Waals (vdW) force have provided a versatile approach for creating hybrid materials and modulating various properties. In this work, the structural and electronic properties of trilayer γ-graphyne, involving different stacking patterns, have been investigated through first-principles approaches. The result indicates that a metal-to-semiconducting transition can be triggered simply by switching the stacking order of trilayer γ-graphyne. More interestingly, in addition to typical vdW homostructures, new 2D carbon allotropes with novel carbon networks can be achieved on the basis of trilayer γ-graphyne, arising from the absence of intralayer acetylene linkages during the structural relaxation. One of the new 2D carbon allotropes possesses an intrinsic semiconducting nature with a wide bandgap of 1.827 eV, coupled with superior structural stability beyond single-layer γ-graphyne. Moreover, the biaxial strain effect on the new 2D carbon allotrope, as well as the trilayer vdW stacks, has also been revealed in this work. Correspondingly, the in-plane tensile strain is demonstrated to further enlarge the electronic bandgaps in these carbon sheets. Therefore, the results of this work imply the great potential of few-layer graphyne in future carbon-based nanoelectronic devices, and simultaneously provide a new approach for developing and synthesizing novel 2D carbon allotropes via the vertical stacking of graphyne with inherent acetylene linkages.

Multibarrier Collaborative Modulation Devices with Ultra-High Logic Operation Density.

The demands for highly miniaturized and multifunctional electronics are rapidly increasing. As scaling-down processes of transistors are restricted by physical limits, reconfigurable electronics with switchable operation functions for different tasks are developed for higher function integration based on split- or vertical-dual-gate structures. To promote the present reconfigurable electronics and exceed the function integration limit, the critical issue is to integrate complex operations into simple circuit forms by establishing more control dimensions. This work proposes a multibarrier collaborative (MBC) modulation architecture to increase the control dimension by multiple forms of potential barriers and achieves combinational and reconfigurable logic operations by a single MBC device. The MBC architecture exhibits ultrahigh logic operation density, including 58.8% area reduction for multiplexer operations and 71.4% area reduction for 4-logic reconfigurable operations. Besides, a hardware security module composed of 4 MBC devices implementing 8 types of logic operations is demonstrated. This work reveals an effective design of function integration for next-generation electronics.

Device simulation study of multilayer MoS2Schottky barrier field-effect transistors.

Molybdenum disulfide (MoS2) is a representative two-dimensional layered transition-metal dichalcogenide semiconductor. Layer-number-dependent electronic properties are attractive in the development of nanomaterial-based electronics for a wide range of applications including sensors, switches, and amplifiers. MoS2field-effect transistors (FETs) have been studied as promising future nanoelectronic devices with desirable features of atomic-level thickness and high electrical properties. When a naturally n-doped MoS2is contacted with metals, a strong Fermi-level pinning effect adjusts a Schottky barrier and influences its electronic characteristics significantly. In this study, we investigate multilayer MoS2Schottky barrier FETs (SBFETs), emphasizing the metal-contact impact on device performance via computational device modeling. We find that p-type MoS2 SBFETs may be built with appropriate metals and gate voltage control. Furthermore, we propose ambipolar multilayer MoS2 SBFETs with asymmetric metal electrodes, which exhibit gate-voltage dependent ambipolar transport behavior through optimizing metal contacts in MoS2 device. Introducing a dual-split gate geometry, the MoS2SBFETs can further operate in four distinct configurations: p - p, n - n, p - n, and n - p. Electrical characteristics are calculated, and improved performance of a high rectification ratio can be feasible as an attractive feature for efficient electrical and photonic devices.

Probing the Nature of Single-Photon Emitters in a WSe2 Monolayer by Magneto-Photoluminescence Spectroscopy.

Monolayer transition metal dichalcogenides (TMDs) have emerged as promising materials to generate single-photon emitters (SPEs). While there are several previous reports in the literature about TMD-based SPEs, the precise nature of the excitonic states involved in them is still under debate. Here, we use magneto-optical techniques under in-plane and out-of-plane magnetic fields to investigate the nature of SPEs in WSe2 monolayers on glass substrates under different strain profiles. Our results reveal important changes on the exciton localization and, consequently, on the optical properties of SPEs. Remarkably, we observe an anomalous PL energy redshift with no significant changes of photoluminescence (PL) intensity under an in-plane magnetic field. We present a model to explain this redshift based on intervalley defect excitons under a parallel magnetic field. Overall, our results offer important insights into the nature of SPEs in TMDs, which are valuable for future applications in quantum technologies.

Recent Advances on Two-Dimensional Nanomaterials Supported Single-Atom for Hydrogen Evolution Electrocatalysts.

Water electrolysis has been recognized as a promising technology that can convert renewable energy into hydrogen for storage and utilization. The superior activity and low cost of catalysis are key factors in promoting the industrialization of water electrolysis. Single-atom catalysts (SACs) have attracted attention due to their ultra-high atomic utilization, clear structure, and highest hydrogen evolution reaction (HER) performance. In addition, the performance and stability of single-atom (SA) substrates are crucial, and various two-dimensional (2D) nanomaterial supports have become promising foundations for SA due to their unique exposed surfaces, diverse elemental compositions, and flexible electronic structures, to drive single atoms to reach performance limits. The SA supported by 2D nanomaterials exhibits various electronic interactions and synergistic effects, all of which need to be comprehensively summarized. This article aims to organize and discuss the progress of 2D nanomaterial single-atom supports in enhancing HER, including common and widely used synthesis methods, advanced characterization techniques, different types of 2D supports, and the correlation between structural hydrogen evolution performance. Finally, the latest understanding of 2D nanomaterial supports was proposed.

Broadband Solar Absorber and Thermal Emitter Based on Single-Layer Molybdenum Disulfide.

In recent years, solar energy has become popular because of its clean and renewable properties. Meanwhile, two-dimensional materials have become a new favorite in scientific research due to their unique physicochemical properties. Among them, monolayer molybdenum disulfide (MoS2), as an outstanding representative of transition metal sulfides, is a hot research topic after graphene. Therefore, we have conducted an in-depth theoretical study and design simulation using the finite-difference method in time domain (FDTD) for a solar absorber based on the two-dimensional material MoS2. In this paper, a broadband solar absorber and thermal emitter based on a single layer of molybdenum disulfide is designed. It is shown that the broadband absorption of the absorber is mainly due to the propagating plasma resonance on the metal surface of the patterned layer and the localized surface plasma resonance excited in the adjacent patterned air cavity. The research results show that the designed structure boasts an exceptional broadband performance, achieving an ultra-wide spectral range spanning 2040 nm, with an overall absorption efficiency exceeding 90%. Notably, it maintains an average absorption rate of 94.61% across its spectrum, and in a narrow bandwidth centered at 303 nm, it demonstrates a near-unity absorption rate, surpassing 99%, underscoring its remarkable absorptive capabilities. The weighted average absorption rate of the whole wavelength range (280 nm-2500 nm) at AM1.5 is above 95.03%, and even at the extreme temperature of up to 1500 K, its heat radiation efficiency is high. Furthermore, the solar absorber in question exhibits polarization insensitivity, ensuring its performance is not influenced by the orientation of incident light. These advantages can enable our absorber to be widely used in solar thermal photovoltaics and other fields and provide new ideas for broadband absorbers based on two-dimensional materials.

Recent Advances in Chemoresistive Gas Sensors Using Two-Dimensional Materials.

Two-dimensional (2D) materials have emerged as a promising candidate in the chemoresistive gas sensor field to overcome the disadvantages of conventional metal-oxide semiconductors owing to their strong surface activities and high surface-to-volume ratio. This review summarizes the various approaches to enhance the 2D-material-based gas sensors and provides an overview of their progress. The distinctive attributes of semiconductor gas sensors employing 2D materials will be highlighted with their inherent advantages and associated challenges. The general operating principles of semiconductor gas sensors and the unique characteristics of 2D materials in gas-sensing mechanisms will be explored. The pros and cons of 2D materials in gas-sensing channels are discussed, and a route to overcome the current challenges will be delivered. Finally, the recent advancements to enhance the performance of 2D-material-based gas sensors including photo-activation, heteroatom doping, defect engineering, heterostructures, and nanostructures will be discussed. This review should offer a broad range of readers a new perspective toward the future development of 2D-material-based gas sensors.

Doping the Spin-Polarized Graphene Minicone on Ni(111).

In the attempt to induce spin-polarized states in graphene (Gr), rare-earth deposition on Gr/Co(0001) has been demonstrated to be a successful strategy: the coupling of graphene with the cobalt substrate provides spin-polarized conical-shaped states (minicone) and the rare-earth deposition brings these states at the Fermi level. In this manuscript, we theoretically explore the feasibility of an analogue approach applied on Gr/Ni(111) doped with rare-earth ions by means of density functional theory calculations. Even if not well mentioned in the literature, this system owns a minicone, similar to the cobalt case. By testing different rare-earth ions, not only do we suggest which one can provide the required doping but we also explain the effect behind this proper charge transfer.

Thermal Relaxation in Janus Transition Metal Dichalcogenide Bilayers.

In this work, we employ molecular dynamics simulations with semi-empirical interatomic potentials to explore heat dissipation in Janus transition metal dichalcogenides (JTMDs). The middle atomic layer is composed of either molybdenum (Mo) or tungsten (W) atoms, and the top and bottom atomic layers consist of sulfur (S) and selenium (Se) atoms, respectively. Various nanomaterials have been investigated, including both pristine JTMDs and nanostructures incorporating inner triangular regions with a composition distinct from the outer bulk material. At the beginning of our simulations, a temperature gradient across the system is imposed by heating the central region to a high temperature while the surrounding area remains at room temperature. Once a steady state is reached, characterized by a constant energy flux, the temperature control in the central region is switched off. The heat attenuation is investigated by monitoring the characteristic relaxation time (τav) of the local temperature at the central region toward thermal equilibrium. We find that SMoSe JTMDs exhibit thermal attenuation similar to conventional TMDs (τav~10-15 ps). On the contrary, SWSe JTMDs feature relaxation times up to two times as high (τav~14-28 ps). Forming triangular lateral heterostructures in their surfaces leads to a significant slowdown in heat attenuation by up to about an order of magnitude (τav~100 ps).

A 2D Optoelectronic Logic Device with Ultralow Supply Voltage.

Optoelectronic logic devices (OELDs) provide a cure for many visually impaired individuals. However, traditional OELDs have limitations, such as excessive channel resistance and complex structure, leading to high supply voltage and decreased efficiency of signal transmission. We report ultralow-voltage OELDs by seriating two 2D MoTe2 transistors with sub-10 nm channel lengths. The short channel length and atomically flat interface result in a low-resistance light-sensing unit that can operate with a low supply voltage and function well in weak-light conditions. The devices achieve an on state without light signal input and an off state with light signal input at an ultralow supply voltage of 50 mV, lower than the retinal bearing voltage of 70 mV. Additionally, MoTe2's excellent optoelectronic properties allow the device to perceive light from visible to near-infrared wavelengths with high sensitivity to weak light signals. The specific perception of visible light intensity is 0.03 mW·mm-2, and the near-infrared light intensity is 0.1 mW mm-2. The device also has a response time of 8 ms, meeting human needs. Our findings provide a promising solution for developing low-voltage artificial retinas.

Codoped germanene with 3p and 4p elements elements.

CONTEXT: The relentless need for new materials to be used in electronic devices has opened new research directions in materials science. One of them involves using two-dimensional materials, among which there is current interest in using germanene. The heteroatom doping of germanene has been proposed as a possible approach to fine-tuning its electronic properties. However, this procedure is complicated because locating the dopants with a specific arrangement is challenging, thus achieving reproducibility. To avoid this problem, we propose the codoping of germanene to understand if dopants prefer to be agglomerated as observed for graphene or if they prefer to adopt a random disposition. Herein, we employed first-principles calculations to study 21 codoped germanene systems with one 3p (Al, Si, P, and S) and one 4p (Ga, As, and Se) element. Our results indicate that in the cases of AlP, AlS, GaP, GaS, GaAs, and GaSe codoped germanene, the dopants show a tendency to be located in specific lattice positions. The ortho disposition of dopants is preferred for AlP, AlS, GaP and GaS codoped germanene and their 4p counterparts GaAs and GaSe codoped germanene, and the materials showed interesting electronic properties making them suitable to develop germanene-based electronic materials. METHODS: We utilized the M06-L, HSE06 methods accompanied by the 6-31G* basis sets to perform periodic boundary conditions calculations as implemented in Gaussian 09. The unit cells were sampled employing 100 k-points for geometry optimizations and 2000 k-points for electronic properties The ultrafine grid was employed. Results were visualized employing Gaussview 5.0.1. In addition to this, we performed B3LYP-D3 periodic calculations as implemented in CRYSTAL17.

Unusual Geometric and Electronic Structures at Domain Boundaries in a Heterochiral Charge Density Wave Superlattice.

Domain boundaries (DBs) in charge density wave (CDW) systems not only are important for understanding the mechanism of how CDW interplays with other quantum phases but also have potential for future CDW-based nanodevices. However, current research on DBs in CDW materials has been mainly limited to those between homochiral CDW domains, whereas DBs between heterochiral CDW domains, especially in the atomic layers, remain largely unexplored. Here, we have studied the geometric and electronic states of heterochiral DBs in single-layer and bilayer 1T-NbSe2 using scanning tunneling microscopy/spectroscopy. We observe the existence of diverse CDW configurations in a single heterochiral CDW DB with atomic resolution and reveal the corresponding electronic states. In addition, interlayer stacking further enriches the electronic properties of the DB. Our results offer deep insights into the relationship between the detailed CDW nanostructures and electronic behaviors, which has significant implications for DB engineering in strongly correlated CDW systems and related nanodevices.

Electronic excitations and spin interactions in chromium trihalides from embedded many-body wavefunctions.

Although chromium trihalides are widely regarded as a promising class of two-dimensional magnets for next-generation devices, an accurate description of their electronic structure and magnetic interactions has proven challenging to achieve. Here, we quantify electronic excitations and spin interactions in CrX 3 (X = Cl, Br, I) using embedded many-body wavefunction calculations and fully generalized spin Hamiltonians. We find that the three trihalides feature comparable d-shell excitations, consisting of a high-spin 4 A 2 ( t 2 g 3 e g 0 ) ground state lying 1.5-1.7 eV below the first excited state 4 T 2 ( t 2 g 2 e g 1 ). CrCl3 exhibits a single-ion anisotropy A sia = - 0.02 meV, while the Cr spin-3/2 moments are ferromagnetically coupled through bilinear and biquadratic exchange interactions of J 1 = - 0.97 meV and J 2 = - 0.05 meV, respectively. The corresponding values for CrBr3 and CrI3 increase to A sia = -0.08 meV and A sia= - 0.12 meV for the single-ion anisotropy, J 1 = -1.21 meV, J 2 = -0.05 meV and J 1 = -1.38 meV, J 2 = -0.06 meV for the exchange couplings, respectively. We find that the overall magnetic anisotropy is defined by the interplay between A sia and A dip due to magnetic dipole-dipole interaction that favors in-plane orientation of magnetic moments in ferromagnetic monolayers and bulk layered magnets. The competition between the two contributions sets CrCl3 and CrI3 as the easy-plane (A sia + A dip >0) and easy-axis (A sia + A dip <0) ferromagnets, respectively. The differences between the magnets trace back to the atomic radii of the halogen ligands and the magnitude of spin-orbit coupling. Our findings are in excellent agreement with recent experiments, thus providing reference values for the fundamental interactions in chromium trihalides.

Tailoring polarization in WSe2 quantum emitters through deterministic strain engineering.

Quantum emitters in transition metal dichalcogenides (TMDs) have recently emerged as a promising platform for generating single photons for optical quantum information processing. In this work, we present an approach for deterministically controlling the polarization of fabricated quantum emitters in a tungsten diselenide (WSe2) monolayer. We employ novel nanopillar geometries with long and sharp tips to induce a controlled directional strain in the monolayer, and we report on fabricated WSe2 emitters producing single photons with a high degree of polarization (99 ± 4%) and high purity (g (2)(0) = 0.030 ± 0.025). Our work paves the way for the deterministic integration of TMD-based quantum emitters for future photonic quantum technologies.

First principles study of BN triphenylene-graphdiyne monolayer and bilayer structures with varying C-chain lengths: insights into optical behavior.

First-principles calculations engaging density functional theory (DFT) are employed to systematically study the optical characteristics of monolayer and bilayer boron nitride (BN) triphenylene-graphdiyne (Tp-BNyne) structures featuring varying lengths of C-chains. The thermal stability of Tp-BNyne structures at temperatures up to 1000 K is verified. The weak van der Waals interactions due to the small binding energies and significant interlayer distances maintain the cohesion between the layers. The investigation revealed that all Tp-BNyne structures under examination exhibit semiconductor behavior with a band gap in the range of 0.97-2.74 eV. The bilayer configurations demonstrated a narrower energy band gap in comparison to the monolayer ones. Increasing the length of C-chains leads to a reduction in the energy band gap. Delving into the optical behavior of Tp-BNyne structures under photon incidence with parallel and perpendicular polarizations, a distinct anisotropy in the optical characteristics of Tp-BNyne is revealed. The static dielectric constant increases and the optical band gap decreases with increasing C-chain length. The absorption coefficients of monolayer and bilayer Tp-BNyne structures, on the order of 107/m, demonstrate that these sheets can effectively absorb light in the visible and ultraviolet regions. These findings present Tp-BNyne sheets as promising candidates for use in photovoltaic devices to convert sunlight into electrical current, as well as for designing optical devices for ultraviolet protection. Additionally, Tp-BNyne structures are transparent materials, especially in the high-energy range.

Deep eutectic Solvents-Assisted synthesis of NiFe-LDHs/Mo2Ti2C3: A bifunctional electrocatalyst for overall electrochemical water splitting in alkaline media.

The development of efficient and stable electrocatalysts is crucial for the advancement of green and clean hydrogen energy technologies. In this work, we synthesized a nanocomposite of nickel-iron layered double hydroxide/molybdenum titanium carbide (NiFe-LDHs/Mo2Ti2C3) using a deep eutectic solvent (DESs) by the solvothermal method. The formation of NiFe-LDHs/Mo2Ti2C3 nanocomposite was confirmed by various electron microscopic and spectroscopic techniques. The synthesized nanocomposite was investigated as a bifunctional electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) under the alkaline condition. The NiFe-LDHs/Mo2Ti2C3-based electrodes exhibit small overpotentials of 204 and 306 mV for HER and OER at a current density of 10 mA cm-2. The anchor of NiFe-LDHs on the surface of Mo2Ti2C3 induces an interfacial synergistic effect, leading to a significantly improvement in electrochemical performance. Remarkably, the proposed NiFe-LDHs/Mo2Ti2C3 modified electrode demonstrates superior performance compared to many recently reported LDHs and MXenes-based electrocatalysts in an alkaline environment. Furthermore, a symmetrical two-electrode water splitting setup employing the NiFe-LDHs/Mo2Ti2C3 electrocatalyst requires an electrolysis voltage of 1.65 V to achieve a current density of 10 mA cm-2. The findings provide a new perspective on the rational design and synthesis of multifunctional electrocatalysts for electrochemical applications.

Design of an Oxide Monolayer with High ZT by a Strong Anharmonicity Unit.

In this paper, a new strategy to obtain a transition-metal oxide (TMO) thermoelectric monolayer is demonstrated. We show that the TMO thermoelectric monolayer can be achieved by the replacement of a transition-metal atom with a cluster, which is composed of heavy transition atoms with abundant valence electrons. Specifically, the transition-metal atom in the XO2 (X = Ti, Zr, Hf) monolayer is replaced by the [Ag6]4+ cluster and a stable structure Ag6O2 is achieved. Due to the abundant valence electrons in the [Ag6]4+ cluster unit, n-type Ag6O2 has high electrical conductivity, which leads to a satisfactory power factor. More importantly, Ag6O2 has an extremely low phonon thermal conductivity of 0.16 W·m-1·K-1, which is one of the lowest values in thermoelectric materials. An in-depth study reveals that the extremely low value originates from the strong phonon anharmonicity and weak metal bond of the [Ag6]4+ cluster unit. Due to the satisfactory power factor and ultralow phonon thermal conductivity, Ag6O2 has high ZT at 300-700 K, and the maximum ZT is 3.77, corresponding to an energy conversion efficiency of 22.24%. Our results demonstrate that replacement of the transition-metal atom by an appropriate cluster is a good way to obtain a TMO thermoelectric monolayer.