Electric Field-Controlled Magneto-Optical Kerr Effect in A-Type Antiferromagnetic Fe2CX2 (X = F, Cl) and Its Janus Monolayer.

The magneto-optical Kerr effect (MOKE) is a powerful probe of magnetism and has recently gained new attention in antiferromagnetic (AFM) materials. Through extensive first-principles calculations and group theory analysis, we have identified Fe2CX2 (X = F, Cl) and Janus Fe2CFCl monolayers as ideal A-type collinear AFM materials with high magnetic anisotropy and Néel temperatures. By applying a vertical external electrical field (Ef) of 0.2 V/Å, the MOKE is activated for Fe2CF2 and Fe2CCl2 monolayers without changing their magnetic ground state, and the maximum Kerr rotation angles are 0.13 and 0.08°, respectively. Due to the out-of-plane spontaneous polarization, the intrinsic and nonvolatile MOKE is found in the Janus Fe2CFCl monolayer and the maximal Kerr rotation angle without external electronic field is 0.25°. Moreover, the intrinsic built-in electronic field also gives origin to more robust A-type AFM ordering and reversible Kerr angle against external Ef. Our study suggests that Ef is an effective tool for controlling MOKE in two-dimensional (2D) AFM materials. This research opens the possibility of related studies and applications in AFM spintronics.

Two-Dimensional Magnetic Semiconducting Heterostructures of Single-Layer CrI3-CrI2.

Single-layer heterostructures of magnetic materials are unique platforms for studying spin-related phenomena in two dimensions (2D) and have promising applications in spintronics and magnonics. Here, we report the fabrication of 2D magnetic lateral heterostructures consisting of single-layer chromium triiodide (CrI3) and chromium diiodide (CrI2). By carefully adjusting the abundance of iodine based on molecular beam epitaxy, single-layer CrI3-CrI2 heterostructures were grown on Au(111) surfaces with nearly atomic-level seamless boundaries. Two distinct types of interfaces, i.e., zigzag and armchair interfaces, have been identified by means of scanning tunneling microscopy. Our scanning tunneling spectroscopy study combined with density functional theory calculations indicates the existence of spin-polarized ground states below and above the Fermi energy localized at the boundary. Both the armchair and zigzag interfaces exhibit semiconducting nanowire behaviors with different spatial distributions of density of states. Our work presents a novel low-dimensional magnetic system for studying spin-related physics with reduced dimensions and designing advanced spintronic devices.

Monolayer Sc2CF2 as a Potential Selective and Sensitive NO2 Sensor: Insight from First-Principles Calculations.

Two-dimensional materials with excellent surface-volume ratios and massive reaction sites recently have been receiving attention for gas sensing. With first-principles calculations, we explored the performance of monolayer Sc2CF2 as a gas sensor. We investigated how molecule adsorption affects its electronic structure and optical properties. It is found that a large charge transfer quantity happens between Sc2CF2 and NO2, which results from the fact that the lowest unoccupied molecular orbital (LUMO) of NO2 is below the valence band maximum (VBM) of Sc2CF2. Moreover, the MD simulation shows that NO2 can adsorb on the Sc2CF2 surface stably at room temperature. We explored the effect of biaxial strain on the adsorption energy and charge transfer quantity of each system, and the results show that the biaxial strain can enhance both the adsorption energy and charge transfer quantity of the NO2 system and thus can improve the sensitivity of Sc2CF2 in detecting the NO2 molecule. Furthermore, we investigated the adsorption behavior and charge transfer of polar polyatomic molecules at the Sc2CF2 surface with h-BN as a substrate, and the results demonstrate that the h-BN substrate can hardly modify the main results. Our result predicts that Sc2CF2 can be a promising selective and sensitive sensor to detect the NO2 molecule, and could also give a theoretical guide for other terminated MXenes used for gas sensors or detectors.

Two-Dimensional Room-Temperature Magnetic Nonstoichiometric Fe7Se8 Nanocrystals: Controllable Synthesis and Magnetic Behavior.

Two-dimensional (2D) magnetic materials have attracted significant attention for promising applications in energy-saving logic and robust memory devices. However, most 2D magnets discovered so far typically feature drawbacks for practical applications due to low critical temperatures. Herein, we synthesize ultrathin room-temperature (RT) magnetic Fe7Se8 nanoflakes via the space-confined chemical vapor deposition method. It is found that the appropriate supply and control of Se concentration in the reaction chamber is crucial for synthesizing high-quality nonstoichiometric Fe7Se8 nanoflakes. Cryogenic electrical and magnetic characterizations reveal the emergence of spin reorientation at ∼130 K and the survival of long-range magnetic ordering up to room temperature. The RT magnetic domain structures with different thicknesses are also uncovered by magnetic force microscopy. Moreover, theoretical calculations confirm the spin configuration and metallic band structure. The outstanding characteristics exhibited by Fe7Se8 nanoflakes, including RT magnetism, spin reorientation property, and good electrical conductivity, make them a potential candidate for RT spintronics.

Photoinduced Spin Injection and Ferromagnetism in 2D Group III Monochalcogenides.

Strong light-matter interactions in low-dimensional materials offer an opportunity for flexible property-tuning by optical switching. Herein, we exploit photoexcitation for spin injection into semiconductors by rationally designing heterojunctions having distinct dynamic behavior for photocarriers in two spin channels. As a proof-of-concept, we trigger homogeneous magnetism in a group III monochalcogenide monolayer (MX with M = In, Ga; X = S, Se) by placing it on a ferromagnetic CrI3 substrate under light illumination. Our time-dependent ab initio nonadiabatic molecular dynamics simulations reveal fast electron-hole separation for the majority spin channel but rapid recombination for the minority spin channel at this heterostructure. The majority carriers cause hole doping and strong ferromagnetic ordering in the MX sheet, with magnetic moment tunable by the injected carriers' concentration. The interplay between photoexcited hole carriers, the Van Hove singularity of MX monolayers, and interfacial charge transfer provides essential physical insights for nondestructively manipulating charge and spin in two-dimensional semiconductors via light switching.

Solar driven CO2 hydrogenation on transition metal doped Zn12O12 cluster.

Photocatalytic hydrogenation of carbon dioxide (CO2) to produce value-added chemicals and fuel products is a critical routine to solve environmental issues. However, developing photocatalysts composed of earth-abundant, economic, and environmental-friendly elements is desired and challenging. Metal oxide clusters of subnanometer size have prominent advantages for photocatalysis due to their natural resistance to oxidation as well as tunable electronic and optical properties. Here, we exploit 3d transition metal substitutionally doped Zn12O12 clusters for CO2 hydrogenation under ultraviolet light. By comprehensive ab initio calculations, the effect of the dopant element on the catalytic behavior of Zn12O12 clusters is clearly revealed. The high activity for CO2 hydrogenation originates from the distinct electronic states and charge transfer from transition metal dopants. The key parameters governing the activity and selectivity, including the d orbital center of TM dopants and the energy level of the highest occupied molecular orbital for the doped Zn12O12 clusters, are thoroughly analyzed to establish an explicit electronic structure-activity relationship. These results provide valuable guidelines not only for tailoring the catalytic performance of subnanometer metal oxide clusters at atomic precision but also for rationally designing non-precious metal photocatalysts for CO2 hydrogenation.

Tuning Schottky barriers for monolayer GaSe FETs by exploiting a weak Fermi level pinning effect.

Monolayer gallium selenide (GaSe), an emerging two-dimensional semiconductor, holds great promise for electronics and optoelectronics. In reality, the contact properties between a semiconductor and the electrodes play a vital role in device performance. Thus, selecting suitable electrode materials with zero contact resistance is critical and challenging. Here, we explore the contact properties and electronic transport of monolayer GaSe with a series of electrode materials (including transition metals and MXenes) by ab initio electronic calculations and quantum transport simulations. Bare MXenes (V2C, Mo2C, Nb2C) and transition metals (Ni, Cu, Pt, Au) form strong chemical bonds with monolayer GaSe and lead to n-type contacts with Schottky barriers of 0-0.53 eV. The O-terminated MXenes (V2CO2 and Nb2CO2) establish van der Waals interactions with the GaSe sheet and form p-type contacts with vanishing hole Schottky barriers but large tunneling barriers. Impressively, Ohmic contact is achieved by the V2C and Mo2C electrodes, which is further demonstrated by the linear I-V curves. These contact systems exhibit a weak Fermi level pinning effect, with Schottky barriers in both the vertical and lateral directions controllable by the work function of the electrodes. To promote the carrier injection process, we propose to select electrode materials with a strong surface polarization and low work function (<5.0 eV) for GaSe-based devices.

Heterostructures of MXenes and N-doped graphene as highly active bifunctional electrocatalysts.

MXenes with versatile chemistry and superior electrical conductivity are prevalent candidate materials for energy storage and catalysts. Inspired by recent experiments of hybridizing MXenes with carbon materials, here we theoretically design a series of heterostructures of N-doped graphene supported by MXene monolayers as bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). Our first-principles calculations show that the graphitic sheet on V2C and Mo2C MXenes are highly active with an ORR overpotential down to 0.36 V and reaction free energies for the HER approaching zero, both with low kinetic barriers. Such outstanding catalytic activities originate from the electronic coupling between the graphitic sheet and the MXene, and can be correlated with the pz band center of surface carbon atoms and the work function of the heterostructures. Our findings screen a novel form of highly active electrocatalysts by taking advantage of the fast charge transfer kinetics and strong interfacial coupling of MXenes, and illuminate a universal mechanism for modulating the catalytic properties of two-dimensional hybrid materials.

Nitrogen-Doped Graphene on Transition Metal Substrates as Efficient Bifunctional Catalysts for Oxygen Reduction and Oxygen Evolution Reactions.

Composites of transition metal and carbon-based materials are promising bifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), and are widely used in rechargeable metal-air batteries. However, the mechanism of their enhanced bicatalytic activities remains elusive. Herein, we construct N-doped graphene supported by Co(111) and Fe(110) substrates as bifunctional catalysts for ORR and OER in alkaline media. First-principles calculations show that these heterostructures possess a large number of active sites for ORR and OER with overpotentials comparable to those of noble metal benchmark catalysts. The catalytic activity is modulated by the coupling strength between graphene and the metal substrates, as well as the charge distribution in the graphitic sheet, which is delicately mediated by N dopants. These theoretical results uncover the key parameters that govern the bicatalytic properties of hybrid materials and help prescribe the principles for designing multifunctional electrocatalysts of high performance.

Gas adsorption on monolayer blue phosphorus: implications for environmental stability and gas sensors.

Monolayer blue phosphorus has recently been synthesized by molecular beam epitaxial growth on Au(111) substrate. It is intriguing to compare this new 2D phase of phosphorus with phosphorene as to both fundamental properties and application prospects. Here, first-principles calculations are carried out to explore the adsorption behaviors of environmental gas molecules on monolayer blue phosphorus, including O2, NO, SO2, NH3, H2O, NO2, CO2, H2S, CO, and N2, and address their effects on the electronic properties of the material. Our calculations show that O2 is prone to dissociate and tends to chemisorb on the blue phosphorus sheet, phenomena which has also been observed in phosphorene. The other gas molecules can stably physisorb on monolayer blue phosphorus, showing different interaction strengths with the monolayer. These molecules induce distinct modifications to the band gap, carrier effective mass, and work function, which also depends on the molecular coverage. The responses of the electronic properties are subject to the charge transfer as well as alignment of the frontier molecular orbital levels of the gaseous molecules and band edges of the parent sheet. These results suggest that monolayer blue phosphorus is a promising candidate for novel gas sensors.