Phase transition in WSe2-xTex monolayers driven by charge injection and pressure: a first-principles study.

Alloying strategies permit new probes for governing structural stability and semiconductor-semimetal phase transition of transition metal dichalcogenides (TMDs). However, the possible structure and phase transition mechanism of the alloy TMDs, and the effect of an external field, have been still unclear. Here, the enrichment of the Te content in WSe2-xTex monolayers allows for coherent structural transition from the H phase to the T' phase. The crystal orbital Hamiltonian population (COHP) uncovers that the bonding state of the H phase approaches the high-energy domain near the Fermi level as the Te concentration increases, posing a source of structural instability followed by a weakened energy barrier for the phase transition. In addition, the structural phase transition driven by charge injection opens up new possibilities for the development of phase-change devices based on atomic thin films. For WSe2-xTex monolayers with the H phase as the stable phase, the critical value of electron concentration triggering the phase transition decreases with an increase in the x value. Furthermore, the energy barrier from the H phase to the T' phase can be effectively reduced by applying tensile strain, which could favor the phase switching in electronic devices. This work provides a critical reference for controllable modulation of phase-sensitive devices from alloy materials with rich phase characteristics.

Recent progress in 2D bipolar magnetic semiconductors.

Bipolar magnetic semiconductor (BMS) is a class of magnetic semiconductors, whose valence band maximum and conduction band minimum are fully spin-polarized with opposite spin directions. Due to the special energy band, half-metallicity can be easily obtained in BMS by gate voltage, and the spin polarization can be reversed between spin-up and down when the gate voltage switches from positive to negative. BMSs have great potential applications in spintronic devices, such as the field-effect spin valves, spin filters and spin transistors,etc. With the rapid progress of the two-dimensional (2D) magnetic materials, researchers have identified a series of potential intrinsic 2D BMS materials using high-throughput computational methods. Additionally, methods such as doping, application of external stress, introduction of external fields, stacking of interlayer antiferromagnetic semiconductors, and construction of Janus structures have endowed existing materials with BMS properties. This paper reviews the research progress of 2D BMS. These advancements provide crucial guidance for the design and synthesis of BMS materials and offer innovative pathways for the future development of spintronics.

Ferromagnetism emerged from non-ferromagnetic atomic crystals.

The recently emerged ferromagnetic two-dimensional (2D) materials provide unique platforms for compact spintronic devices down to the atomic-thin regime; however, the prospect is hindered by the limited number  of ferromagnetic 2D materials discovered with limited choices of magnetic properties. If 2D antiferromagnetism could be converted to 2D ferromagnetism, the range of 2D magnets and their potential applications would be significantly broadened. Here, we discovered emergent ferromagnetism by interfacing non-magnetic WS2 layers with the antiferromagnetic FePS3. The WS2 exhibits an order of magnitude enhanced Zeeman effect with a saturated interfacial exchange field ~38 Tesla. Given the pristine FePS3 is an intralayer antiferromagnet, the prominent interfacial exchange field suggests the formation of ferromagnetic FePS3 at interface. Furthermore, the enhanced Zeeman effect in WS2 is found to exhibit a strong WS2-thickness dependence, highlighting the layer-tailorable interfacial exchange coupling in WS2-FePS3 heterostructures, which is potentially attributed to the thickness-dependent interfacial hybridization.

Optically Induced Multistage Phase Transition in Coherent Phonon-Dominated a-GeTe.

Ultrafast photoexcitation can decouple the multilevel nonequilibrium dynamics of electron-lattice interactions, providing an ideal probe for dissecting photoinduced phase transition in solids. Here, real-time time-dependent density functional theory simulations combined with occupation-constrained DFT methods are employed to explore the nonadiabatic paths of optically excited a-GeTe. Results show that the short-wavelength ultrafast laser is capable of generating full-domain carrier excitation and repopulation, whereas the long-wavelength ultrafast laser favors the excitation of lone pair electrons in the antibonded state. Photodoping makes the double-valley potential energy surface shallower and allows the insertion of A1g coherent forces in the atomic pairs, by which the phase reversal of Ge and Te atoms in the ⟨001⟩ direction is activated with ultrafast suppression of the Peierls distortion. These findings have far-reaching implications regarding nonequilibrium phase engineering strategies based on phase-change materials.

Ta4C3-Modulated MOF-Derived 3D Crosslinking Network of VO2(B)@Ta4C3 for High-Performance Aqueous Zinc Ion Batteries.

A two-dimensional MXene (Ta4C3) was innovatively used herein to modulate the space group and electronic properties of vanadium oxides, and the MXene/metal-organic framework (MOF) derivative VO2(B)@Ta4C3 with 3D network cross-linking was prepared, which was then employed as a cathode to improve the performance of aqueous zinc ion batteries (ZIBs). A novel method combining HCl/LiF and hydrothermal treatments was used to etch Ta4AlC3 to obtain a large amount of accordion-like Ta4C3, and the V-MOF was then hydrothermally grown on the surface of the stripped Ta4C3 MXene. During the annealing process of V-MOF@Ta4C3, the addition of Ta4C3 MXene liberates the V-MOF from agglomerative stacking, allowing it to show additional active sites. More significantly, Ta4C3 prevents the V-MOF in the composite structure from converting into V2O5 of space group Pmmn but into VO2(B) of space group C2/m after annealing. A considerable advantage of VO2(B) for Zn2+ intercalation is provided by the negligible structural transformation during the intercalation process and the special tunnel transport channels, which have an enormous area (0.82 nm2 along the b axis). According to first-principles calculations, there is a strong interfacial interaction between VO2(B) and Ta4C3, which deliver remarkable electrochemical activity and kinetic performances for the storage of Zn2+. Therefore, the ZIBs prepared with the VO2(B)@Ta4C3 cathode material exhibit an ultra-high capacity of 437 mA h·g-1 at 0.1 A·g-1 while showing good cycle performance and dynamic performance. This study will offer a fresh approach and a reference for creating metal oxide/MXene composite structures.

Ferroelectric control of band alignments and magnetic properties in the two-dimensional multiferroic VSe2/In2Se3.

Our first-principles evidence shows that the two-dimensional (2D) multiferroic VSe2/In2Se3experiences continuous change of electronic structures, i.e. with the change of the ferroelectric (FE) polarization of In2Se3, the heterostructure can possess type-I, -II, and -III band alignments. When the FE polarization points from In2Se3to VSe2, the heterostructure has a type-III band alignment, and the charge transfer from In2Se3into VSe2induces half-metallicity. With reversal of the FE polarization, the heterostructure enters the type-I band alignment, and the spin-polarized current is turned off. When the In2Se3is depolarized, the heterostructure has a type-II band alignment. In addition, influence of the FE polarization on magnetism and magnetic anisotropy energy of VSe2was also analyzed, through which we reveal the interfacial magnetoelectric coupling effects. Our investigation about VSe2/In2Se3predicts its wide applications in the fields of both 2D spintronics and multiferroics.

Comparative Raman spectroscopy of magnetic topological material EuCd2X2(X=P, As).

EuCd2X2(X = P, As) is a new class of magnetic topological materials discovered recently. The electronic structure and the band topology are intimately coupled with its magnetism, giving rise to interesting properties such as spin fluctuation and colossal magnetoresistance. Phonon excitation can contribute to the quasi-particle response of the topological matters through spin-lattice and electron-phonon coupling. However, the phonon properties of this material family remain unexplored. Here we report a comparative study of Raman-active vibration modes in EuCd2X2(X = P, As) by means of angle-resolved, temperature-resolved, and magnetic-field-resolved Raman spectroscopy together with the first-principle calculations and Raman tensor analysis. The phonon properties can be tuned by chemical potential and temperature within the material family. All the phonon modes are softened with increased chemical pressure by replacing P with As. Angle-resolved polarized Raman spectroscopy reveals the configuration-sensitive Raman activity and the isotropic intensity response. In addition, the magneto-Raman spectrum indicates the stability of Raman-active vibration modes against the magnetic field at room temperature. Our work sheds light on the phonon dynamics of magnetic topological matters, which are potentially coupled with the topological charge and spin excitation.

Oxygen-Terminated Nb2CO2 MXene with Interfacial Self-Assembled COF as a Bifunctional Catalyst for Durable Zinc-Air Batteries.

The desirable air cathode in Zn-air batteries (ZABs) that can effectively balance oxygen evolution and oxygen reduction reactions not only needs to adjust the electronic structure of the catalyst but also needs a unique physical structure to cope with the complex gas-liquid environment. In this work, first-principles calculations were carried out to prove that oxygen-terminated Nb2CO2 MXene played an active role in enhancing the sluggish reaction of oxygen intermediates. Nb2CO2 MXene could also stimulate the spatial accumulation of discharge products, which was beneficial to improve the stability of secondary ZABs. Molecular dynamics simulation was used to show that the confinement effect of COF could effectively regulate the concentration of O2 on the surface of Nb2CO2@COF, which was conducive to an efficient and durable reaction. COF-LZU1 was self-assembled on the interface of Nb2CO2 MXene (Nb2CO2@COF) for the first time. The Nb2CO2@COF electrode had excellent OER/ORR overpotentials with the potential difference (ΔE) of 0.79 V. When applied to the configuration of ZABs, Nb2CO2@COF showed a power density of 75 mW cm-2 and favorable long-term charge/discharge stability, so it could be used as a potential candidate cathode for noble-metal-based catalysts. This idea of combining MXenes and COFs sheds some light on the design of ZABs.

Electric control of nearly free electron states and ferromagnetism in the transition-metal dichalcogenides monolayers.

Using the first-principles calculations, we explore the nearly free electron (NFE) states in the transition-metal dichalcogenidesMX2(M= Mo, W;X= S, Se, Te) monolayers. It is found that both the external electric field and electron (not hole) injection can flexibly tune the energy levels of the NFE states, which can shift down to the Fermi level and result in novel transport properties. In addition, we find that the valley polarization can be induced by both electron and hole doping in MoTe2monolayer due to the ferromagnetism induced by the charge injection, which, however, is not observed in other five kinds ofMX2monolayers. We carefully check band structures of all theMX2monolayers, and find that the exchange splitting in the top of the valence band and the bottom of conduction band plays the key role in the ferromagnetism. Our researches enrich the electronic, spintronic, and valleytronic properties ofMX2monolayers.

Cu3BiS3/MXenes with Excellent Solar-Thermal Conversion for Continuous and Efficient Seawater Desalination.

Two-dimensional materials with unique physical and chemical properties have recently attracted widespread attention in the field of solar thermal conversion. However, affected by the Fresnel effect, traditional two-dimensional materials such as MXenes, graphene, transition metal disulfide often have relatively significant light reflection losses at the solid-liquid or gas interface. So how to improve the light absorption of the two-dimensional material performance has become a new challenge in photothermal conversion. Here, we use an improved thermal-injection method to uniformly grow Tricopper(I) Bismuth Sulfide (Cu3BiS3, CBS) on the surface of Ti3C2 nanosheets in a nonaqueous polar solvent environment. A three-dimensional nanoflower-nanosheet structure CBS-Ti3C2 for photothermal conversion has been constructed successfully. Owing to the excellent photothermal performance of Cu3BiS3 in the near-infrared region, the good thermal conductivity of Ti3C2, and the unique porous structure of the composite material, the composite achieves broadband absorption of light (more than 90% in the visible light region, more than 80% in the near-infrared region), which optical model and finite element simulation have theoretically verified. The composite material has obtained higher solar-to-heat conversion performance than similar material systems, and the steady-state temperature can reach 62.3 °C under 1 sun incident light intensity. CBS-Ti3C2 is expected to become a light-absorbing layer material for solar vapor generation devices due to its excellent light-to-heat conversion performance and good material flexibility. It still guarantees a reasonably high steam generation rate (1.32 kg·m-2·h-1) even with a thinner material thickness (0.48 mg·cm-2) and a comprehensive conversion efficiency higher than 90%. Besides, CBS-Ti3C2 also exhibits the characteristics of resisting surface salt accumulation, which is conducive to maintaining the long-lasting photothermal seawater evaporation process. The material's electronic structure and the charge transfer process of the heterojunction interface have been studied with the first-principles calculation. The high light absorption performance and good thermal conductivity of the composite material are theoretically explained and supported.

Vanadium based carbide-oxide heterogeneous V2O5@V2C nanotube arrays for high-rate and long-life lithium-sulfur batteries.

Due to their ultra-high theoretical energy density, low cost, and environmental friendliness, lithium-sulfur batteries have become a potentially strong competitor for next-generation energy storage devices. The search for a host material that can effectively anchor sulfur to a cathode to solve the adverse effects of the shuttle effect on batteries has become a research hotspot in the academic world. Here, we propose a three-dimensional heterostructure of V2O5 nanotube arrays vertically grown on V2C-MXenes as a sulfur-supporting host material for the cathode of lithium-sulfur batteries. Through first-principles calculations, we found that V2O5@V2C exhibits an extreme adsorption capacity for polysulfides. Besides, thanks to the excellent catalytic performance of V2O5 for oxidation reactions, the conversion reaction potential of polysulfides to Li2S and Li2S2 is significantly reduced, and the shuttle effect of lithium-sulfur batteries is effectively suppressed. Also, the larger specific surface area and tubular structure of the composite host material can increase the sulfur loading of the cathode while ensuring the stability of the electrode structure. The V2O5@V2C/S electrode exhibits higher initial capacity (1173 mA h g-1 at 0.2C), longer cycle life (1000 cycles with 0.047% decay per period), and higher sulfur loading (8.4 mg cm-2). We believe that this work can provide a reference for the design of cathode host materials for lithium-sulfur batteries with long cycle life.

Dipole control of Rashba spin splitting in a type-II Sb/InSe van der Waals heterostructure.

InSe monolayer, belonging to group III-VI chalcogenide family, has shown promising performance in the realm of spintronic. Nevertheless, the out-of-plane mirror symmetry in InSe monolayer constrains the electrons' degrees of freedom, and this will confine its spin-related applications. Herein, we construct Sb/InSe van der Waals heterostructure to extend the electronic and spintronic properties of InSe. The density functional theory is utilized to verify the tunable electronic properties and Rashba spin splitting (RSS) of Sb/InSe heterostructure. According to the obtained results, the Sb/InSe heterostructure can be considered as a direct band gap semiconductor with typical type-II band alignment, where the electrons and holes are localized in the InSe and Sb layers, respectively. The RSS is recognized at conduction band minimum around Γ point in Sb/InSe, which is induced by the spontaneous internal electric field with electric dipole moment of 0.016 e Å from Sb to InSe. The vertical strain, in-plane strain, and external electric field are employed to modulate the strength of RSS. The Rashba coefficient and dipole moment exhibit the similar variation tendency, suggesting the strength of RSS depends on the magnitude of dipole moment. The controllable RSS makes Sb/InSe heterostructure become an appropriate candidate material for spintronic devices.

The InSe/SiH type-II van der Waals heterostructure as a promising water splitting photocatalyst: a first-principles study.

Photocatalytic water splitting for hydrogen production has attracted increasing research attention in recent years, and great efforts have been made in order to find the ideal photocatalyst. In this work, we proposed a two-dimensional material-based van der Waals (vdW) heterostructure constructed by vertically stacked indium selenide (InSe) and silicane (SiH) and studied the feasibility of using it as a possible photocatalyst for water splitting by using first-principles methods. The results show that the InSe/SiH is a direct band gap semiconductor with appropriate gap value and band edge position for photocatalysts in water splitting. Importantly, this heterostructure presents type-II band alignment at the equilibrium configuration, which supports the effective separation of photoexcited electrons and holes. A built-in electric field set up within the interface of the heterostructure will further hinder the electron-hole recombination and thus improve the photocatalytic efficiency. In addition, compared with separated InSe and SiH monolayers, the heterostructure exhibits enhanced light absorption capabilities in ultraviolet and visible light regions. These findings indicate that the InSe/SiH vdW heterostructure is a promising candidate for photocatalysts for solar water splitting.

Ferroelectric Switching of Pure Spin Polarization in Two-Dimensional Electron Gas.

Two-dimensional electron gas (2DEG) created at compound interfaces can exhibit a broad range of exotic physical phenomena, including quantum Hall phase, emergent ferromagnetism, and superconductivity. Although electron spin plays key roles in these phenomena, the fundamental understanding and application prospects of such emergent interfacial states have been largely impeded by the lack of purely spin-polarized 2DEG. In this work, by first-principles calculations of the multiferroic superlattice GeTe/MnTe, we find the ferroelectric polarization of GeTe is concurrent with the half-metallic 2DEG at interfaces. Remarkably, the pure spin polarization of the 2DEG can be created and annihilated by polarizing and depolarizing the ferroelectrics and can be switched (between pure spin-up and pure spin-down) by flipping the ferroelectric polarization. Given the electric-field amplification effect of ferroelectric electronics, we envision multiferroic superlattices could open up new opportunities for low-power, high-efficiency spintronic devices such as spin field-effect transistors.

Remarkable Rashba spin splitting induced by an asymmetrical internal electric field in polar III-VI chalcogenides.

Herein, the Rashba spin orbit coupling (SOC) of polar group III-VI chalcogenide XABY (A, B = Ga, In; X ≠ Y = S, Se, Te) monolayers is investigated based on density functional theory. The different electronegativities of X and Y atoms lead to an asymmetrical internal electric field in the XABY monolayer; this implies that the internal electric field between A and X is not equal to that between B and Y. Mirror symmetry breaking in the XABY monolayer induces a remarkable Rashba spin splitting (RSS) at the conduction band minimum (CBM). Moreover, it is demonstrated that an external electric field and an in-plane biaxial strain can affect the internal electric field by varying the charge distribution, and this further manipulates the RSS. Under a positive external electric field and tensile strain, the RSS at the CBM exhibits a near-linear increasing behavior, whereas under a negative external electric field and compressive strain, the RSS displays a monotonous decreasing pattern. In addition, we explored the influence of interlayer coupling and substrate on the RSS. The stacking pattern of bilayer structures has a significant impact on the RSS. The investigation of SInGaSe on the Si(111) substrate suggests that the Rashba band is situated inside the large band gap of the substrate. Overall, our investigations suggest that the polar group III-VI chalcogenides are promising candidates for future spintronic applications.

Electric field control of Rashba spin splitting in 2D NIIIXVI (N = Ga, In; X = S, Se, Te) monolayer.

Spin splitting of the nonmagnetic two dimensional (2D) layered NIIIXVI (N = Ga, In; X = S, Se, Te) monolayer is investigated based on the density functional theory. Due to the mirror symmetry, there is no Rashba spin splitting (RSS) in the freestanding NX plane. It is found that applying the external electric field perpendicular to the NX plane can result in sizable RSS around the Γ point due to the mirror symmetry breaking. The induced RSS is mainly influenced by the anions X and gradually strengthens with the increase of external electric field. The considerable RSS is observed in NTe systems. Moreover, the influence of in-plane biaxial strain on RSS is explored, and the tensile strain can enhance the RSS, especially for those bands around the Fermi level. Our theoretical investigation provides a deep insight in spin splitting behaviors in NX monolayers and agrees well with the experimental report.

MoB2: a new multifunctional transition metal diboride monolayer.

Several layered transition metal borides can now be realized by a simple and general fabrication method (Fokwa et al 2018 Adv. Mater. 30 1704181), inspiring our interest to transition metal borides monolayer. Herein, we predict a new two-dimensional (2D) transition metal diboride MoB2 monolayer (ML) and study its intrinsic mechanical, thermal, electronic, and transport properties. The MoB2 ML has isotropic mechanic properties along the zigzag and armchair directions with a large Young's stiffness, and has an ultralow room-temperature thermal conductivity. The Mo atoms dominate the metallic nature of MoB2 ML. It shows an obvious electrical anisotropy and a current-limiting behavior. Our findings suggest that MoB2 ML is a promising multifunctional material used in ultrathin high-strength mechanical materials, heat insulating materials, electrical-anisotropy-based materials, and current limiters. It is helpful for the experimentalists to further prepare and utilize the transition metal diboride 2D materials.

Ferroelectric and dipole control of band alignment in the two dimensional InTe/In2Se3 heterostructure.

Two dimensional (2D) ferroelectric materials are gaining growing attention due to their nontrival ferroelectricity, and the 2D ferroelectric heterostructures with tunable electronic, optoelectronic, or even magnetic properties, show many novel properties that do not exist in their constituents. In this work, by using the first-principles calculations, we investigate the ferroelectric and dipole control of electronic structures of the 2D ferroelectric heterostructure InTe/In2Se3. It is found that band alignment is closely dependent on the ferroelectric polarization of In2Se3. By switching the polarization of In2Se3, the band alignment of InTe/In2Se3 switches from a staggered (type II) to a straddling type (type I), and the band gap changes from indirect gap 0.76 eV to direct gap 0.15 eV. When the ferroelectric field of In2Se3 is reversed, the band alignment of InTe/In2Se3 switches from type-I to type-II, and the band gap changes from indirect gap 0.76 eV to direct gap 0.15 eV. In addition, we find that the interlayer dipole can also effectively modulate the band structure and induce the type-I to type-II band alignment transition. Our present results indicate that the 2D ferroelectric heterostructure with the tunable band alignment and band gap can be of great significance in the optoelectronic devices.

Electric manipulation of magnetism in bilayer van der Waals magnets.

The ferromagnetism of the two dimensional (2D) Cr2Ge2Te6 atomic layers with the perpendicular magnetic anisotropy and the Curie temperature 30-50 K has recently been experimentally confirmed. By performing the density-functional theory calculations, we demonstrate that the magnetic properties of bilayer Cr2Ge2Te6 can be flexibly tailored, due to the effective band structure tuning by the external electric field. The electric field induces the semiconductor-metal transition and redistributes charge and spin between the two layers. Furthermore, the magnetic anisotropy energy of the bilayer Cr2Ge2Te6 can be obviously enhanced by the electric field, which is helpful to stabilize the long-range ferromagnetic order. Our study about the electric manipulation of magnetism based on the band structure engineering generally exists in 2D magnetic systems and will be of great significance in low-dimensional all-electric spintronics.

First-principles investigation of the interface magnetic anisotropy of Fe/SrTiO3.

Interface effects in magnetic nanostructures play a critical role in the magnetic properties. By using first-principles density functional theory calculations, we investigate the electronic and magnetic properties of Fe/SrTiO3 interfaces, in which both the nonpolar surface SrTiO3(0 0 1) and the polar surface SrTiO3(1 1 0) are considered. A particular emphasis is placed on the magnetic anisotropy energy (MAE). Comparing MAE of the Fe/SrTiO3 interfaces and the corresponding Fe monolayers, we find the Fe/SrTiO3(0 0 1) interface decreases MAE, while the Fe/SrTiO3(1 1 0) interface increases MAE. The interface orbital hybridization and orbital magnetic moments are analyzed in detail to understand the different interface magnetic anisotropy. Our investigation indicates that interface engineering can be an effective way to modulate the magnetic properties.