Janus Monolayer Research Articles

Electronic and optical properties of two-dimensional Janus Sn0.5Ge0.5S monolayer

Janus two-dimensional (2D) materials have received widespread attention in recent years due to their out-of-plane asymmetric structures which makes them promising candidates for sustainable energy devices. In this work, using first-principles calculations, we study a novel 2D Janus monolayer Sn0.5Ge0.5S for recently synthesized SnS monolayer. We investigate structural, electronic and optical properties of this new 2D Janus material. Our results show that monolayer Sn0.5Ge0.5S is an indirect band gap semiconductor with the lowest conduction band is nearly flat around the band minimum. Atom projected band structure reveals that this flattened valley is mainly originated from orbitals of Sn atom. In addition, the inclusion of spin–orbit coupling leads to splitting of the bands, largely along Γ-Y direction. Optical absorption spectra indicate superior sunlight absorption in the visible and ultraviolet regions. Interestingly, absorption spectra of Janus monolayer Sn0.5Ge0.5S are polarization dependent owing to its anisotropic crystal structure along zigzag and armchair directions.

The origin of anomalous mass-dependence of thermal conductivity in Janus XBAlY (X = Se, S, Te; Y = S, Se, O; X ≠ Y) monolayers

Owing to the unique asymmetric geometry, Janus monolayer compounds exhibit various exotic thermal properties and have promising applications in thermal management. In this study, we combine machine learning potentials and the phonon Boltzmann transport equation to perform a comparative study of the thermal transport properties in Janus XBAlY (X = Se, S, Te; Y = S, Se, O; X ≠ Y) monolayers. Our findings unveil a thermal conductivity (κp) ranking as SeBAlS > TeBAlO > SBAlSe, contradicting the conventional expectation that a higher κp is typically observed when the average atomic mass is smaller. At room temperature, the κp of SeBAlS is 174 Wm−1 K−1, which is 4.8 times that of SBAlSe when considering three-phonon scattering processes. Moreover, the consideration of four-phonon scatterings does not alter such ranking. The anomalous κp phenomenon was explained through a detailed analysis of the phonon–phonon scattering mechanism, phonon bandgap, phonon anharmonicity, and chemical bond strength. This study highlights the intricate relationship between atomic mass, bonding characteristics, and thermal properties, offering insights for designing Janus materials with tailored thermal conductivity.

Novel Janus monolayer 1T'-MoSF features robust stability and superior mechanical flexibility

Janus monolayers of transition-metal dichalcogenides (TMDs) have garnered significant attention in various scientific fields due to their exceptional physical properties. Among the known Janus monolayer TMDs, MoSX holds particular significance, with X typically representing chalcogen atoms. The successful synthesis of MoSH has pushed the boundaries of X beyond the conventional chalcogens. Nevertheless, it remains an open question whether other elements can also yield stable Janus monolayer MoSX. Herein, we employ theoretical methods to undertake a comprehensive evaluation of the stability of Janus monolayer MoSX (X = Li, Be, B, C, N, F, Na, Mg, Al, Si, P, Cl). The analysis of stability encompasses various aspects, including energetic, mechanical, dynamical, and thermodynamic features. Interestingly, our investigations have revealed the existence of a hitherto undiscovered stable 1T'-MoSF structure. Remarkably, this structure exhibits significant anisotropy, providing superior mechanical flexibility due to its low Young’s modulus. In addition, despite the dynamical instability of 2H/1T-MoSN and the mechanical instability of 2H/1T-MoSC/Mg, they could potentially exist under specific conditions. This theoretical study not only provides insights into the structural characteristics and stability of novel Janus monolayer MoSX, but also extends the Janus monolayer MoSX family, which would be valuable to future applications of Janus TMDs.

Superconductivity and electron self-energy in tungsten-sulfur-hydride monolayer

Hydrogen-rich structures have recently gained attention as a candidate for room-temperature superconductors. Hydrogen has high phonon frequencies and can be an ideal component for superconductors if it also exhibits strong electron–phonon coupling. In bulk materials, this has been achieved only under very high pressure. Two-dimensional hydrogen-decorated materials can also be expected to become superconductors. Recently, it was shown that a Janus MoSH monolayer can be synthesized (Lu et al 2017 Nat. Nanotechnol. 12 744–9), and a theoretical investigation of this MoSH monolayer claimed that T c = 28.58 K at atmospheric pressure (Liu et al 2022 Phys. Rev. B 105 245420). In this work, we propose that tungsten sulfur hydride (WSH) is also a superconducting Janus monolayer. The Tc is carefully calculated with very high resolution via the Eliashberg spectral function and the electron self-energy. We find that WSH is a conventional BCS superconductor with T c = 12.2 K at ambient pressure. For practical applications, sensitive dependence on substrate is inferred. We also reported the electron self-energy of WSH, which can be compared directly with future measurements from angle-resolved photoelectron spectroscopy.

Direct Exchange in Ultra‐Thin Ferromagnetic Janus MXenes

The development of spintronic devices urgently requires ultra‐thin two‐dimensional (2D) ferromagnetic materials with high Curie temperature (Tc), TC however, there are few natural intrinsic ferromagnetic 2D materials. The successful synthesis of Janus monolayer MoSSe in experiments provides a new approach for designing new 2D materials. By replacing transition metal carbides with two different transition metal atoms, we have designed over 70 Janus MXence materials and determined that 30+ materials have ferromagnetic ground states, of which three have robust ferromagnetism through density functional theory analysis. The ferromagnetic coupling in such materials mainly originates from the direct exchange of d‐orbitals between transition metal atoms in different layers. Further, using K‐nearest neighbours (KNN) machine learning (ML) method, six out of the remaining 360 Janus MXence systems were screened for ferromagnetism, with one system exhibiting strong ferromagnetism. This work provides an alternative and convenient method for developing ultra‐thin 2D magnetic materials for next generation spintronic device applications.

Computational insight on transport properties of Re-doped Janus monolayer WSeTe

Designing a stable two-dimensional (2D) n-type semiconductor with a wider bandgap and higher carrier conductivity could be a promising material for advanced transport device applications. In this study, we design experimentally synthesized Janus monolayer WSeTe and use ab-initio-based density functional theory combined with Boltzmann transport theory to explore charge carrier anisotropy in mobility. We emphasise structural and transport properties in terms of scattering information to modulate the transport mechanisms in computing carrier mobility and electrical conductivity. We also substitute Re in WSeTe to optimize carrier concentration which eventually increases electrical conductivity in Re0.5W0.5SeTe. Thus, our findings on new 2D materials used in nanoelectronics should encourage researchers to explore innovative energy materials with higher bandgap without compromising electrical conductivity.

Janus monolayer PXC (X = As/Sb) for photocatalytic water splitting with a negative Poisson's ratio.

Two-dimensional (2D) Janus materials have attracted considerable attention in photocatalysis owing to their robust redox capability and efficient segregation. In this study, we propose a novel Janus monolayer structure, denoted as PXC (X = As/Sb), exhibiting favorable stability in terms of dynamics, thermal properties, and mechanical characteristics. The PXC monolayers demonstrate a relatively smaller Young's modulus (132.5/119.5 N m-1 for PAsC/PSbC) and large negative Poisson's ratios (-0.15/-0.101 for PAsC/PSbC). Moreover, the HSE06 + SOC functional results show that PAsC/PSbC are indirect semiconductors with a 2.33/1.43 eV band gap, exhibiting a suitable band alignment for photocatalytic water splitting. The calculated high carrier mobility (104 cm2 V-1 s-1), along with a significant discrepancy, determined by the deformation potential theory and the built-up field induced by the large intrinsic dipole, effectively suppresses the recombination of photogenerated carriers. Furthermore, PXC monolayers possess a strong absorption capacity in the visible and ultraviolet light region (105 cm-1). Therefore, our results indicate that PXC monolayers hold great potential for application in the field of photocatalytic water splitting.

First-principles studies on the electronic and contact properties of monolayer Ga2STe-metal contacts.

Monolayer (ML) Janus III-VI compounds have attracted the use of multiple competitive platforms for future-generation functional electronics, including non-volatile memories, field effect transistors, and sensors. In this work, the electronic and interfacial properties of ML Ga2STe-metal (Au, Ag, Cu, and Al) contacts are systematically investigated using first-principles calculations combined with the non-equilibrium Green's function method. The ML Ga2STe-Au/Ag/Al contacts exhibit weak electronic orbital hybridization at the interface, while the ML Ga2STe-Cu contact exhibits strong electronic orbital hybridization. The Te surface is more conducive to electron injection than the S surface in ML Ga2STe-metal contact. Quantum transport calculations revealed that when the Te side of the ML Ga2STe is in contact with Au, Ag and Cu electrodes, p-type Schottky contacts are formed. When in contact with the Al electrode, an n-type Schottky contact is formed with an electron SBH of 0.079 eV. When the S side of ML Ga2STe is in contact with Au and Al electrodes, p-type Schottky contacts are formed, and when it is in contact with Ag and Cu electrodes, n-type Schottky contacts are formed. Our study will guide the selection of appropriate metal electrodes for constructing ML Ga2STe devices.

Novel valley character and tunable quasi-half-valley metal state in Janus monolayer VSiGeP4.

The manipulation and regulation of valley characteristics have aroused widespread interest in emerging information fields and fundamental research. Realizing valley polarization is one crucial issue for spintronic and valleytronic applications, the concepts of a half-valley metal (HVM) and ferrovalley (FV) materials have been put forward. Then, to separate electron and hole carriers, a fresh concept of a quasi-HVM (QHVM) has been proposed, in which only one type of carrier is valley polarized for electron and hole carriers. Based on first-principles calculations, we demonstrate that the Janus monolayer VSiGeP4 has QHVM character. To well regulate the QHVM state, strain engineering is utilized to adjust the electronic and valley traits of monolayer VSiGeP4. In the discussed strain range, monolayer VSiGeP4 always favors the ferromagnetic ground state and out-of-plane magnetization, which ensures the appearance of spontaneous valley polarization. It is found that the QHVM state can be induced in different electronic correlations (U), and the strain can effectively tune the valley, magnetic, and electronic features to maintain the QHVM state under various U values. Our work opens up a new research idea in the design of multifunctional spintronic and valleytronic devices.

Strain-induced topological phase transition in ferromagnetic Janus monolayer MnSbBiS2Te2.

We investigate a strain-induced topological phase transition in the ferromagnetic Janus monolayer MnSbBiS2Te2 using first-principles calculations. The electronic, magnetic, and topological properties are studied under biaxial strain within the range of -8 to +8%. The ground state of monolayer MnSbBiS2Te2 is metallic with an out-of-plane magnetic easy axis. A band gap is opened when a compressive strain between -4% and -7% is applied. We observe a topological phase transition at a biaxial strain of -5%, where the material becomes a Chern insulator exhibiting a quantum anomalous hall (QAH) effect. We find that biaxial strain and spin-orbit coupling (SOC) are responsible for the topological phase transition in MnSbBiS2Te2. In addition, we find that biaxial strain can alter the direction of the magnetic easy axis of MnSbBiS2Te2. The Curie temperature is calculated using the Heisenberg model and is found to be 24 K. This study could pave the way to the design of topological materials with potential applications in spintronics, quantum computing, and dissipationless electronics.

Tunable abundant valley Hall effect and chiral spin-valley locking in Janus monolayer VCGeN4.

It is both conceptually and practically fascinating to explore fundamental research studies and practical applications of two-dimensional systems with the tunable abundant valley Hall effect. In this work, based on first-principles calculations, the tunable abundant valley Hall effect is proved to appear in Janus monolayer VCGeN4. When the magnetization is along the out-of-plane direction, VCGeN4 is an intrinsic ferromagnetic semiconductor with a valley feature. The intriguing spontaneous valley polarization exists in VCGeN4 due to the common influence of broken inversion and time-reversal symmetries, which makes it easier to realize the anomalous valley Hall effect. Furthermore, we observe that the valley-non-equilibrium quantum anomalous Hall effect is driven by external strain, which is located between two half-valley-metal states. When reversing the magnetization, the spin flipping makes the position of the edge state to change from one valley to another valley, demonstrating an intriguing behavior known as chiral spin-valley locking. Although the easy magnetic axis orientation is along the in-plane direction, we can utilize an external magnetic field to transform the magnetic axis orientation. Moreover, it is found that the valley state, electronic and magnetic properties can be well regulated by the electric field. Our works explore the mechanism of the tunable abundant valley Hall effect by applying an external strain and electric field, which provides a perfect platform to investigate the spin, valley, and topology.

Novel C4P2 monolayers: forming Z-scheme heterojunction and Janus structure for high-efficiency metal-free photocatalytic water splitting.

Metal-free two-dimensional (2D) semiconductors have garnered significant attention in the realm of photocatalytic water splitting, primarily owing to their inherent clean, stable, and efficient photoresponsive properties. Motivated by it, we have proposed two types of stable C4P2 monolayers with indirect band gaps, mediocre carrier mobility and excellent optical absorption in visible-light and ultraviolet regions. Although the too-low work function of monolayer α-C4P2 and the too-high work function of monolayer β-C4P2 make them only suitable for single-side redox reaction in photocatalytic water splitting, the creation of an α-C4P2/β-C4P2 Z-scheme heterojunction, combined with the Janus monolayer γ-C4P2 that integrates features of both α and β structures, effectively addresses this limitation, fulfilling the prerequisites for comprehensive photocatalytic water splitting. Furthermore, the calculations indicate that the α-C4P2/β-C4P2 Z-scheme heterojunction and Janus monolayer γ-C4P2 not only demonstrate improved carrier mobility and optical absorption but also feature internal electric fields that effectively enhance driving energy and photo-induced charge separation. Notably, Janus monolayer γ-C4P2 achieves a high electron mobility of ∼105 cm2 V-1 s-1 and an impressive solar-to-hydrogen conversion efficiency of 25.62%.

Metallic CoSb and Janus Co2AsSb monolayers as promising anode materials for metal-ion batteries.

Structural symmetry breaking plays a pivotal role in fine-tuning the properties of nano-layered materials. Here, based on the first-principles approaches we propose a Janus monolayer of metallic CoSb by breaking the out-of-plane structural symmetry. Specifically, within the CoSb monolayer by replacing the top-layer 'Sb' with 'As' atoms entirely, the Janus Co2AsSb monolayer can be formed, whose structure is confirmed via structural optimization and ab initio molecular dynamics simulations. Notably, the Janus Co2AsSb monolayer demonstrates stability at an elevated temperature of 1200 K, surpassing the stability of the CoSb monolayer, which remains stable only up to 900 K. We propose that both the CoSb and Janus Co2AsSb monolayers could serve as capable anode materials for power-driven metal-ion batteries, owing to their substantial theoretical capacity and robust binding strength. The theoretical specific capacities for Li/Na reach up to 1038.28/1186.60 mA h g-1 for CoSb, while Janus Co2AsSb demonstrates a marked improvement in electrochemical storage capacity of 3578.69/2215.38 mA h g-1 for Li/Na, representing a significant leap forward in this domain. The symmetry-breaking effect upgrades the CoSb monolayer, as a more viable contender for power-driven metal-ion batteries. Furthermore, electronic structure calculations indicate a notable charge transfer that augments the metallic nature, which would boost electrical conductivity. These simulations demonstrate that the CoSb and Janus Co2AsSb monolayers have immense potential for application in the design of metal-ion battery technologies.

Multipiezo Effect in Altermagnetic V2SeTeO Monolayer.

Strain engineering has been used as an efficient method to modulate various properties of quantum materials and electronic devices. One may establish piezo effects based on a disciplined response to the strain in multifunctional nanosystems. Inspired by a recent theoretical proposal on the interesting piezomagnetism and C-paired valley polarization in the V2Se2O monolayer, we predict a stable altermagnetic Janus monolayer V2SeTeO using density functional theory calculations. It exhibits a novel "multipiezo" effect combining piezoelectricity, piezovalley, and piezomagnetism. Most interestingly, the valley polarization and the net magnetization under strain in V2SeTeO exceed these in V2Se2O, along with the additional large piezoelectric coefficient. The "multipiezo" effect makes Janus monolayer V2SeTeO as a tantalizing material for potential applications in nanoelectronics, optoelectronics, spintronics, and valleytronics.

Investigation of Atomic‐Scale Mechanical Behavior by Bias‐Induced Degradation in Janus and Alloy Polymorphic Monolayer TMDs via In Situ TEM

The 2D Janus transition‐metal dichalcogenides (TMDs) and alloyed TMDs are a widely studied emerging class of 2D materials that have been extensively used in electronic devices because of their excellent electronic, optical, and mechanical properties. The properties and behaviors of 2D‐materials‐based devices, such as the electrical breakdown caused by structural failure, are significant issues that have drawn considerable attention. In this study, the electrical behavior of polymorphic molybdenum sulfide selenide (MoSSe) devices is studied via in situ biasing experiments and recorded using transmission electron microscopy (TEM) at the atomic scale. The selenization temperature is a key factor in the phase transition of the material, which further affects the electrical and mechanical properties of MoSSe. The effects of electron‐beam irradiation and bias voltage are also discussed through a combination of experiments and theory. Quantifying the defect coverage and defect size also helps us to understand the behavior of material degradation. Furthermore, Cs‐corrected scanning TEM is utilized to identify the evolution of the morphology. The fracture morphology of the synthesized structure also varies with the application of high voltage. The cracks and defects caused by Joule heating are studied in terms of fracture type and size.

Dzyaloshinskii–Moriya Interaction of Cr2O2ClI Janus Monolayer: A First‐Principles Calculation

The Dzyaloshinskii–Moriya interactions (DMIs) of Cr2O2ClI Janus monolayer are investigated using the first‐principles calculations. There are three DMI mechanisms (namely, the Half–Fert–Levy mechanism, the Fert–Levy mechanism, and the Rashba mechanism) in Cr2O2ClI Janus monolayer. The Half–Fert–Levy mechanism, by which the I atoms enhance the spin orbit coupling interaction on the type‐I Cr atoms but have no such effect on the type‐II Cr atoms, contributes to the y‐component of the DMI vector between two nearest‐neighbor Cr atoms. Originating from the strong spin orbit coupling interaction of the I atoms, the Fert–Levy mechanism results in a significant DMI vector via the Cr–I–Cr exchange path between two type‐I next‐nearest‐neighbor Cr atoms. Induced by the intrinsic electric field of the Janus structure, the Rashba mechanism results in nonzero in‐plane components of the DMI vectors. This work provides the first‐principles calculations of the DMIs of Cr2O2ClI Janus monolayer and reveals insight into the physics behind the calculated DMIs, which promote the understanding of the complicated DMIs due to multiple mechanisms in 2D magnetic Janus monolayers.

Defect engineered Janus MoXTe (X=S, Se) monolayers for hydrogen evolution reaction: A first principles study

Given the elevated expense and constrained accessibility of platinum, the primary catalyst employed in electrocatalytic hydrogen evolution, it becomes essential to pinpoint an alternative catalyst demonstrating exceptional catalytic efficacy and broader scalability potential. In this study, we undertook an exhaustive inquiry into the electrocatalytic activity concerning hydrogen evolution of the monolayer Janus MoXTe (where X represents S and Se) utilizing first-principle calculation. Furthermore, an evaluation of the performance of defective MoXTe structures was conducted. Our findings illuminate that the incorporation of non-metallic elements like B, C, N, and P into MoXTe can be employed to finely adjust the Gibbs free energy (ΔGH) to approximately 0 eV. Particularly, the doping of B and P into the 1T phase of MoSTe (1T-MoSTe-B@ represents 1T phase of MoSTe-B@ and 1T-MoSTe-P@ represents 1T phase of MoSTe-P@), the doping of P into the 1T′ phase of MoSTe (1T′ phase of MoSTe-P@), and the doping of P into the 1T′ phase of MoSeTe (1T′ phase of MoSeTe-P@) exhibit ΔGH values that are in close proximity to zero (ΔGH = 0.02, −0.03, 0.06, and −0.14 eV, respectively). Through further analysis, we found that the pristine and defective structures all exhibit metallic properties. And the doping of P improved HER performance more effectively among four nonmetallic dopants. In details, H get 0.21, 0.29, 0.43 and 0.28 e on doping of B and P into 1T phase MoSTe (1T phase of MoSTe-B@ and 1T phase of MoSTe-P@) and the doping of P into 1T′ phase MoSeTe (1T’ phase of MoSeTe-P@). This study provides strategies for the design of MoXTe monolayer electrocatalysts, and it is expected to be applied to HER catalysts in affordable and efficient manner.

Controllable structure-engineered janus and alloy polymorphic monolayer transition metal dichalcogenides by plasma-assisted selenization process toward high-yield and wafer-scale production

Two-dimensional (2D) materials with an asymmetric structure like Janus transition metal dichalcogenides (TMDCs) exhibit intriguing electronic and optical properties, which can be used for numerous novel electronic and optoelectronic devices application. However, despite tremendous efforts, the synthesis technology of Janus TMDs has not been fully established, especially for high-yield and wafer-scale production. Here, we demonstrate the synthesis of Janus MoSSe by a top-down method for high-yield and wafer-scale production. In particular, we replace the top S atom of monolayer (ML) molybdenum disulfide (MoS2) with Se by controlled vertical plasma-assisted selenization process (PASP). We first synthesized ML Janus MoSSe flakes through PASP. A set of microscopies, spectroscopies and electrical measurements showed that low synthesis temperature (200 °C) leads to the formation of ML Janus MoSSe flake while high temperatures (400 °C and 600 °C) lead to the formation of polymorphic alloy MoSSe flakes. Furthermore, we show that Janus WSSe can likewise be obtained by PASP, indicating the universality of the process. To demonstrate the feasibility of PASP for wafer-scale production of Janus MoSSe, we perform the exact same process but with continuous ML MoS2 on 2-in. sapphire. Our synthesis approach provides a new scalable route to synthesize Janus TMDs toward future electronics.

Electronic Structure and Magnetic Anisotropy Response of Janus Monolayer VSeTe

Herein, the electronic and magnetic properties of the 2D Janus monolayer VSeTe are computed based on first‐principles calculations. The structure stability plays a crucial role in real application for magnetic devices; it is found that the VSeTe favors 2H structure due to non‐negative frequencies in the phonon spectra. The VSeTe monolayer possesses a semiconductor nature with a bandgap of 1.03 eV (0.85 eV) for spin‐up (down) channels. Interestingly, it is shown in the computed results that VSeTe monolayer is a magnetic semiconductor with a magnetic moment of 1.00 . Additionally, the realization of magnetic anisotropy energy can pave the way to utilize VSeTe monolayer for applications in magnetic semiconductor devices.

Stable Janus monolayer MoSHx (0.5 ≤ x ≤ 2)

MoSH is a representative example of a Janus two-dimensional monolayered system consisting of a molybdenum atomic layer sandwiched between sulfur and hydrogen atomic layers. Extensive experimental and theoretical efforts have suggested the great promise of the MoSH material, but the validity of the MoSH model (with a Mo–S–H ratio of 1:1:1) remains uncertain. While various experiments have established the Mo-to-S ratio to be close to 1:1, the hydrogen content has remained elusive even with the use of state-of-the-art characterization techniques due to its lightweight nature. In this study, we present a theoretical investigation aiming to determine the positions and ratios of the hydrogen atoms on MoSHx (with x ranging from 0 to 3) as well as assess their structural stability. By evaluating the energetic, mechanical, and thermodynamic properties, we confirm the existence of stable MoSHx structures within a critical range of hydrogen atom ratios, specifically 0.5 ≤ x ≤ 2.0. Additionally, as the hydrogen atom ratio increases, we observe a transition in the preferred adsorption sites of hydrogen atoms from the center of the hexagonal ring composed of molybdenum and sulfur atoms to the upper region of the molybdenum atoms. This study offers critical insight into the structural characteristics and stability of Janus monolayer MoSHx, contributing to the advancement and application of Janus MoSHx in various fields.