Transition Metal (Co, V, W, Zr) Single-Atom Decorated Biphenylene for Enhancing the Sensing Performance of SF6 Decomposition Molecules.

The highly sensitive gas sensors used to monitor the decomposition of toxic gases in the dielectric materials of electrical equipment are vital in preventing safety problems arising from corrosion of the equipment. Recently, biphenylene (BPN) has been prepared through surface interpolymer hydrofluorination (HF zipper) reaction, whereas potential gas-sensitive devices based on the BPN monolayer have lacked in-depth investigation. The stable geometries, adsorption energies, interlayer distances, and charge transfers of small molecules of toxic gases (H2S, SO2, SOF2, SO2F2) produced by SF6 chalcogenide molecules of decomposition adsorbed on the original BPN monolayer are systematically researched by using nonequilibrium Green's function methods and density functional theory. The results indicated that all small molecules adsorbed on the BPN monolayer are physisorbed, while the type of adsorption turned from physisorption to chemisorption when BPN carried out adsorption with adsorbing a transition metal atom (TMA). In addition, the characteristics of current-voltage (I-V) curves of H2S and SO2 based on the TMA-BPN gas sensors revealed that the currents in BPN-based gas sensors displayed an obvious anisotropy, and the currents in the zigzag direction are larger than that in the armchair orientation regardless of the molecular adsorption cases. Moreover, the difference of currents for TMA-decorated BPN sensors changed more remarkably before and after the adsorption of H2S and SO2 in the zigzag direction. This work offers insights into the design of gas-sensitive devices through the adsorption of small molecules on the TMA-decorated BPN monolayer.

Studying the Adsorption of Gas Molecules and Defects on Modulating the Electronic Transport Characteristics of Monolayer Penta-BN2-Based Devices.

Two-dimensional atomic layer materials, as an important part of the post-Moore era, have recently become an ideal choice for the preparation of high-efficiency, low-power, and miniaturized gas sensors. In this work, our study utilized density functional theory and the nonequilibrium Green's function method to investigate the electronic properties of the pentagonal BN2 (P-BN2) monolayer, as well as its gas-sensing properties for organic and inorganic gases. We also investigated how defects affect the quantum transport properties of the P-BN2-based device. Our findings demonstrate that the CO, H2S, NH3, SO2, C2H5OH, C3H6OH, CH3OH, and CH4 undergo physisorption on the P-BN2 monolayer, while NO, NO2, C2H2, C2H4, and HCHO undergo chemisorption. Then, we analyzed the impact of gas molecules chemisorbed on the P-BN2 monolayer on the electronic transport properties of the P-BN2-based gas sensor. When these five gas molecules are adsorbed, the current of the P-BN2-based gas sensor is greatly reduced. In addition, the effect of defects on the quantum transport properties of the P-BN2-based device is investigated. The results indicate that defects of N, B, and BN atoms lead to a decrease in the current of P-BN2-based nanodevices. Moreover, both the adsorption of gas molecules and the formation of vacancy defects leading to a decrease in device current can be revealed by the local device density of states near the zero-bias Fermi level, elucidating their microscopic mechanisms. Finally, gas molecules can also cause a decrease in the current of defect systems. These theoretical studies are of great significance for exploring two-dimensional atomic layer materials as high-efficiency gas sensors.

High gas sensing performance of inorganic and organic molecule sensing devices based on the BC3N2 monolayer.

Recently, a novel two-dimensional (2D) BC3N2 monolayer has gained a lot of attention due to its graphene-like structure, and it was first reported by using the particle swarm optimization algorithm and ab initio calculations. Combining density functional theory with the non-equilibrium Green's function method, a 2D BC3N2-based nanodevice has been theoretically constructed and the gas sensing performance of the BC3N2 monolayer for inorganic and organic molecules has been extensively investigated. The results revealed that the BC3N2 monolayer remains metallic with thermodynamic stability. Meanwhile, the results of sensing performance analysis show that the inorganic molecules CO, NO, and NO2 and organic molecules C2H2 and HCHO have strong chemical interactions with BC3N2 and were chemically adsorbed onto BC3N2. In contrast, the interactions between NH3, SO2, CH4, C2H4 and CH3OH and BC3N2 are very weak and these molecules adopt physical adsorption. In the case of chemisorption, the electronic transport behaviors of the 2D BC3N2 devices are sensitive to molecules, and the gas sensitivity of BC3N2 is strongly anisotropic, especially for organic C2H2 with the gas sensing ratios from 7.30 to 10.43 (from 2.51 to 2.79) under different bias voltages along the zigzag (armchair) direction. For inorganic molecules, the gas sensing device is not particularly sensitive, and the maximum gas sensing ratio is only 1.36 for CO. Meanwhile, the large anisotropic gas sensitivity can reach up to 2.66/6.22 for electron transport along the armchair and zigzag directions for CO/C2H2 in the BC3N2-based sensing devices. Accordingly, the high gas sensitivity can be disclosed by displaying the scattering state around the Fermi level at different bias voltages during the transport process. As a result, BC3N2 could be used in 2D gas sensing devices, especially for sensing organic molecule C2H2.

Electric-field-controlled electronic structures and quantum transport in monolayer InSe nanoribbons.

Electronic structures and quantum transport properties of the monolayer InSe nanoribbons are studied by adopting the tight-binding model in combination with the lattice Green function method. Besides the normal bulk and edge electronic states, a unique electronic state dubbed as edge-surface is found in the InSe nanoribbon with zigzag edge type. In contrast to the zigzag InSe nanoribbon, a singular electronic state termed as bulk-surface is observed along with the normal bulk and edge electronic states in the armchair InSe nanoribbons. Moreover, the band gap, the transversal electron probability distributions in the two sublayers, and the electronic state of the topmost valence subband can be manipulated by adding a perpendicular electric field to the InSe nanoribbon. Further study shows that the charge conductance of the two-terminal monolayer InSe nanoribbons can be switched on or off by varying the electric field strength. In addition, the transport of the bulk electronic state is delicate to even a weak disorder strength, however, that of the edge and edge-surface electronic states shows a strong robustness against to the disorders. These findings may be helpful to understand the electronic characteristics of the InSe nanostructures and broaden their potential applications in two-dimensional nanoelectronic devices as well.

Tunable electronic properties and optoelectronic characteristics of MoGe2N4/SiC van der Waals heterostructure.

The assembly of van der Waals (vdW) heterostructure with easily regulated electronic properties provides a new way for the expansion of two-dimensional materials and promotes the development of optoelectronics, sensors, switching devices and other fields. In this work, a systematic investigation of the electronic properties of MoGe2N4/SiC heterostructures using density functional theory has been conducted, along with the modulation of electronic properties by vertical strain and the potential application prospects in optoelectronic devices. The results show that MoGe2N4/SiC heterostructure has excellent dynamic and thermal stability and belongs to type-II band alignment semiconductors. This is extremely beneficial for the separation of photo-generating electron-hole pairs, so it has important significance for the development of photovoltaic materials. In addition, under the control of vertical strain, the semiconductor-metal transition occurs in the MoGe2N4/SiC heterostructure when the compressive strain reaches 6%. In the case of compressive strain less than 6% and tensile strain, the MoGe2N4/SiC heterostructure maintains the type-II band alignment semiconductor characteristics. Meanwhile, we find that the MoGe2N4/SiC heterostructure has optical absorption coefficients of up to 105in the visible and ultraviolet light ranges, which can improve the absorption coefficients of the MoGe2N4and SiC monolayer in some visible light regions. Finally, the optical conductivity of the MoGe2N4/SiC heterostructure exhibits significant anisotropy, with the armchair direction displaying higher conductivity within the orange light range. In conclusion, the formation of vdW heterostructure by vertically stacking MoGe2N4and SiC monolayers can effectively improve their electronic and optical properties, which provides a valuable reference for the future development of electronic devices and photovoltaic materials.

Nonvolatile Electrical Control and Reversible Gas Capture by Ferroelectric Polarization Switching in 2D FeI2/In2S3 van der Waals Heterostructures.

Nonvolatile electrical control is the core of future magnetoelectric nanodevices. In this work, we systematically explore both the electronic structures and transport properties of multiferroic van der Waals (vdW) heterostructures consisting of a ferromagnetic FeI2 monolayer and a ferroelectric In2S3 monolayer using density functional theory and the nonequilibrium Green's function method. The results reveal that the FeI2 monolayer can be reversibly switched between semiconducting and half-metallic properties by nonvolatile control of the In2S3 ferroelectric polarization states. Correspondingly, the proof-of-concept two-probe nanodevice based on the FeI2/In2S3 vdW heterostructure exhibits a significant valving effect by modulating the ferroelectric switching. Moreover, it is also found that the preference of nitrogen-containing gases such as NH3, NO, and NO2 for adsorption on the surface of FeI2/In2S3 vdW heterostructures strongly depends on the polarization direction of the ferroelectric layer. In particular, the FeI2/In2S3 heterostructure shows reversible capture behavior for NH3. As a result, the FeI2/In2S3 vdW heterostructure-based gas sensor demonstrates high selectivity and sensitivity. These findings may open up a new route for the application of multiferroic heterostructures to spintronics, nonvolatile memories, and gas sensors.

rh-In2O3 Nanoparticles for Efficient Photocatalytic Degradation of Rifampin.

Photodegradation, a widely accepted and promising technology, has gained significant attention for addressing the escalating concerns of environmental deterioration. In this article, rhombohedral corundum-type In2O3 nanocrystals were obtained from the transformation of InOOH via a simple calcining process. Under ultraviolet light irradiation, they showed higher photocatalytic activity in the decomposition of rifampin compared to that of the cubic phase In2O3 and P25-TiO2. Furthermore, the probable pathway and the feasible mechanism for the degradation of rifampin were also deeply explored and discussed.

A Comparative Study of the Electronic Transport and Gas-Sensitive Properties of Graphene+, T-graphene, Net-graphene, and Biphenylene-Based Two-Dimensional Devices.

The electronic transport properties of the four carbon isomers: graphene+, T-graphene, net-graphene, and biphenylene, as well as the gas-sensing properties to the nitrogen-based gas molecules including NO2, NO, and NH3 molecules, are systematically studied and comparatively analyzed by combining the density functional theory with the nonequilibrium Green's function. The four carbon isomers are metallic, especially with graphene+ being a Dirac metal due to the two Dirac cones present at the Fermi energy level. The two-dimensional devices based on these four carbon isomers exhibit good conduction properties in the order of biphenylene > T-graphene > graphene+ > net-graphene. More interestingly, net-graphene-based and biphenylene-based devices demonstrate significant anisotropic transport properties. The gas sensors based on the above four structures all have good selectivity and sensitivity to the NO2 molecule, among which T-graphene-based gas sensors are the most prominent with a maximum ΔI value of 39.98 µA, being only three-fifths of the original. In addition, graphene+-based and biphenylene-based gas sensors are also sensitive to the NO molecule with maximum ΔI values of 29.42 and 25.63 µA, respectively. However, the four gas sensors are all physically adsorbed for the NH3 molecule. By the adsorption energy, charge transfer, electron localization functions, and molecular projection of self-consistent Hamiltonian states, the mechanisms behind all properties can be clearly explained. This work shows the potential of graphene+, T-graphene, net-graphene, and biphenylene for the detection of toxic molecules of NO and NO2.

High switching ratio and inorganic gas sensing performance in BeN4based nanodevice: a first-principles study.

Recently, Dirac material BeN4has been synthesized by using laser-heated diamond anvil-groove technology (Bykovet al2021Phys. Rev. Lett.126175501). BeN4layer, i.e. beryllonitrene, represents a qualitatively class of two-dimensional (2D) materials that can be built of a metal atom and polymeric nitrogen chains, and hosts anisotropic Dirac fermions. Enlighten by this discovered material, we study the electronic structure, anisotropic transport properties and gas sensitivity of 2D BeN4using the density functional theory combined with non-equilibrium Green's function method. The results manifest that the 2D BeN4shows a typical semi-metallic property. The electronic transport properties of the intrinsic BeN4devices show a strong anisotropic behavior since electrons transmitting along the armchair direction is much easier than that along the zigzag direction. It directly results in an obvious switching characteristic with the switching ratio up to 105. Then the adsorption characteristics indicate that H2S, CO, CO2and H2molecules are physisorption, while the NH3, NO, NO2, SO2molecules are chemisorption. Among these chemisorption cases, the 2D gas sensor devices show an extremely high response for SO2recognition, and the high anisotropy of the original 2D BeN4device still maintains after adsorbing gas molecules. Finally, high switching ratio and inorganic gas sensing performance of BeN4monolayer could be clearly understood with local density of states, bias-dependent spectra, scattered state distribution. In general, the results indicate that the designed BeN4devices have potential practical application in high-ratio switching devices and high gas-sensing molecular devices.

Edge Doping Engineering of High-Performance Graphene Nanoribbon Molecular Spintronic Devices.

We study the quantum transport properties of graphene nanoribbons (GNRs) with a different edge doping strategy using density functional theory combined with nonequilibrium Green's function transport simulations. We show that boron and nitrogen edge doping on the electrodes region can substantially modify the electronic band structures and transport properties of the system. Remarkably, such an edge engineering strategy effectively transforms GNR into a molecular spintronic nanodevice with multiple exceptional transport properties, namely: (i) a dual spin filtering effect (SFE) with 100% filtering efficiency; (ii) a spin rectifier with a large rectification ratio (RR) of 1.9 ×106; and (iii) negative differential resistance with a peak-to-valley ratio (PVR) of 7.1 ×105. Our findings reveal a route towards the development of high-performance graphene spintronics technology using an electrodes edge engineering strategy.

Rectifying Performance of Heterojunction Based on α-Borophene Nanoribbons with Edge Passivation.

We propose a planar model heterojunction based on α-borophene nanoribbons and study its electronic transport properties. We respectively consider three types of heterojunctions. Each type consists of two zigzag-edge α-borophene nanoribbons (Z αBNR), one is metallic with unpassivated or passivated edges by a hydrogen atom (1H-Z αBNR) and the other is semiconducting with the edge passivated by two hydrogen atoms (2H-Z αBNR) or a single nitrogen atom (N-Z αBNR). Using the first-principles calculations combined with the nonequilibrium Green's function, we observe that the rectifying performance depends strongly on the atomic structural details of a junction. Specifically, the rectification ratio of the junction is almost unchanged when its left metallic ribbon changes from ZBNR to 1H-Z αBNR. However, its ratio increases from 120 to 240 when the right semiconducting one varies from 2H-Z αBNR to N-Z αBNR. This rectification effect can be explained microscopically by the matching degree the electronic bands between two parts of a junction. Our findings imply that the borophene-based heterojunctions may have potential applications in rectification nano-devices.

Analytical study on strain tunable electronic structure and optical transitions in armchair black phosphorene nanoribbons.

We theoretically investigate the electronic structure and optical absorption spectrum of armchair-edged black phosphorene nanoribbons (APNRs) with and without uniaxial strain based on the tight-binding Hamiltonian and Kubo formula. We analytically obtain the energy spectrum and wavefunction, and reveal the band gap scaling law as 1/(N + 1)2 for APNRs in the presence and absence of uniaxial strain, where N is the number of armchair dimer across the ribbon. We find the band gap of APNRs linearly increases (decreases) with increasing in-plane uniaxial tensile (compressive) strain ɛ x/y , but shows contrary dependence on the out-of-plane uniaxial strain ɛ z . The effective mass versus strain exhibits the same behavior to that of band gap but with nonlinear dependence. Under an incident light linearly-polarized along the ribbon, we demonstrate that the inter-band optical transitions obey the selection rule Δn = n - n' = 0, but the intra-band transitions are forbidden for both pristine and strained APNRs originating from the orthogonality between the transverse wavefunctions of the sublattices belonging to different subbands. Importantly, the transverse electric field or impurities can release the optical selection rules by breaking the wavefunction orthogonality, which results in that the optical transitions between any subbands are all possible. Our findings provide further understanding on the electronic and optical properties of APNRs, which may pave the way for designing optoelectronic devices based on phosphorene.

Probing the anisotropy of Landau levels in phosphorene by magneto-capacitance with a parabolic potential confinement.

We theoretically investigate the Landau levels (LLs) and magneto-capacitance (MC) of monolayer black phosphorus under a perpendicular magnetic field, on which a parabolic potential is applied along with the armchair and zigzag directions, respectively. By both analytically perturbative calculation and numerical diagonalization based on an effective k ⋅ p Hamiltonian, we find that the LLs parabolically depend on the wave vectors and show strong anisotropy as the parabolic potential is applied along with different crystal directions. Specifically, the analytical LLs obtained by perturbative calculation from a decoupled single-band Hamiltonian are in good agreement with the numerical results. Importantly, the LLs are no longer linearly dependent on the magnetic field and level index even in the low energy regime due to the confinement of parabolic potential which repaints the cyclotron orbits. Moreover, the MC spectrum clearly reflects the structure of the LLs and exhibits strong anisotropic oscillating patterns. It can be used to determine the band parameters of phosphorene, i.e., the effective masses and inter-band coupling in the absence of magnetic and electric fields.

Electric-Controlled Valley Pseudomagnetoresistance in Graphene with Y-Shaped Kekulé Lattice Distortion.

We propose a new method for regulating valley pseudomagnetoresistance in ballistic graphene-based valley field-effect transistors by taking into account the Y-shaped Kekulé lattice distortion and electric barrier. The device involves valley injection and valley detection by ferromagnetic-strain source and drain. The valley manipulation in the channel is achieved via the Y-shaped Kekulé lattice distortion and electric barrier. The central mechanism of these devices lies on Y-shaped Kekulé lattice distortion in graphene can induce a valley precession, thus controlling the valley orientation of channel electrons and hence the current collected at the drain. We found that the tuning external bias voltage makes the valley pseudomagnetoresistance oscillate between positive and negative values and colossal tunneling valley pseudomagnetoresistance of over 30,000% can be achieved. Our results suggest that the synergy of valleytronics and digital logics may provide new paradigms for valleytronic-based information processing and reversible computing.

Electric Field Controlled Indirect-Direct-Indirect Band Gap Transition in Monolayer InSe.

Electronic structures of monolayer InSe with a perpendicular electric field are investigated. Indirect-direct-indirect band gap transition is found in monolayer InSe as the electric field strength is increased continuously. Meanwhile, the global band gap is suppressed gradually to zero, indicating that semiconductor-metal transformation happens. The underlying mechanisms are revealed by analyzing both the orbital contributions to energy band and evolution of band edges. These findings may not only facilitate our further understanding of electronic characteristics of layered group III-VI semiconductors, but also provide useful guidance for designing optoelectronic devices.

Valley precession and valley polarization in graphene with inter-valley coupling.

We theoretically investigate the valley precession and valley polarization in graphene under inter-valley coupling. Our results show that the inter-valley coupling can induce valley polarization in graphene and also precess valleys in real space in a manner similar to the Rashba spin-orbit interaction rotating spins. Moreover, using strain modulation, we can achieve high valley polarization with large valley-polarized currents. These findings provide a new way to create and manipulate valley polarization in graphene.

Helical edge states and edge-state transport in strained armchair graphene nanoribbons.

A helical type edge state, which is generally supported only on graphene with zigzag boundaries, is found to also appear in armchair graphene nanoribbons in the presence of intrinsic spin-orbit coupling and a suitable strain. At a critical strain, there appears a quantum phase transition from a quantum spin Hall state to a trivial insulator state. Further investigation shows that the armchair graphene nanoribbons with intrinsic spin-orbit coupling, Rashba spin-orbit coupling, effective exchange fields and strains also support helical-like edge states with a unique spin texture. In such armchair graphene nanoribbons, the spin directions of the counterpropogating edge states on the same boundary are always opposite to each other, while is not conserved and the spins are canted away from the -direction due to the Rashba spin-orbit coupling, which is different from the case of the zigzag graphene nanoribbons. Moreover, the edge-state energy gap is smaller than that in zigzag graphene nanoribbons, even absent in certain cases.

Edge states and quantum phase transition in graphene under in-plane effective exchange fields.

We investigated the edge states and quantum phase transition in graphene under an in-plane effective exchange field. The result shows that the combined effects of the in-plane effective exchange field and a staggered sublattice potential can induce zero-energy flat bands of edge states. Such flat-band edge states can evolve into helical-like ones in the presence of intrinsic spin-orbit coupling, with a unique spin texture. We also find that the bulk energy gap induced by the spin-orbit coupling and staggered sublattice potential can be closed and reopened with the in-plane effective exchange field, and the reopened bulk gap can be even larger than that induced by only the spin-orbit coupling and staggered sublattice potential, which is different from the case of an out-of-plane effective exchange field. The calculated spin-dependent Chern numbers suggest that the bulk gap closing and reopening is accompanied by a quantum phase transition from a trivial insulator phase across a metal phase into a spin-dependent quantum Hall phase.

Tunable Dirac points and high spin polarization in ferromagnetic-strain graphene superlattices.

Spin-dependent energy bands and transport properties of ferromagnetic-strain graphene superlattices are studied. The high spin polarization appears at the Dirac points due to the presence of spin-dependent Dirac points in the energy band structure. A gap can be induced in the vicinity of Dirac points by strain and the width of the gap is enlarged with increasing strain strength, which is beneficial for enhancing spin polarization. Moreover, a full spin polarization can be achieved at large strain strength. The position and number of the Dirac points corresponding to high spin polarization can be effectively manipulated with barrier width, well width and effective exchange field, which reveals a remarkable tunability on the wavevector filtering behavior.

Full Valley and Spin Polarizations in Strained Graphene with Rashba Spin Orbit Coupling and Magnetic Barrier.

We propose a graphene-based full valley- and spin-polarization device based on strained graphene with Rashba spin orbit coupling and magnetic barrier. The underlying mechanism is the coexistence of the valley and single spin band gaps in a certain Fermi energy. By aligning the Fermi energy in the valley and single spin band gaps, remarkable valley- and spin-polarization currents can be accessed.