Monolayer Arsenene Research Articles

Diffusion quantum Monte Carlo and density functional calculations of the structural stability of bilayer arsenene.

We have studied the structural stability of monolayer and bilayer arsenene (As) in the buckled (b) and washboard (w) phases with diffusion quantum Monte Carlo (DMC) and density functional theory (DFT) calculations. DMC yields cohesive energies of 2.826(2) eV/atom for monolayer b-As and 2.792(3) eV/atom for w-As. In the case of bilayer As, DMC and DFT predict that AA-stacking is the more stable form of b-As, while AB is the most stable form of w-As. The DMC layer-layer binding energies for b-As-AA and w-As-AB are 30(1) and 53(1) meV/atom, respectively. The interlayer separations were estimated with DMC at 3.521(1) Å for b-As-AA and 3.145(1) Å for w-As-AB. A comparison of DMC and DFT results shows that the van der Waals density functional method yields energetic properties of arsenene close to DMC, while the DFT + D3 method closely reproduced the geometric properties from DMC. The electronic properties of monolayer and bilayer arsenene were explored with various DFT methods. The bandgap values vary significantly with the DFT method, but the results are generally qualitatively consistent. We expect the present work to be useful for future experiments attempting to prepare multilayer arsenene and for further development of DFT methods for weakly bonded systems.

Superconductivity in Li-intercalated bilayer arsenene and hole-doped monolayer arsenene: a first-principles prediction

Using first-principles calculations, we find Li-intercalated bilayer arsenene with AB stacking is dynamically stable, which is different from pristine bilayer with AA stacking. Electron–phonon coupling of the stable Li-intercalated bilayer arsenene are dominated by the low frequency vibrational modes (E″(1), (1), E′(1) and acoustic modes) and lead to an superconductivity with Tc = 8.68 K with isotropical Eliashberg function. Small biaxial tensile strain (2%) can improve Tc to 11.22 K due to the increase of DOS and phonon softening. By considering the fully anisotropic Migdal–Eliashberg theory, Tc are found to be enhanced by 50% and exhibits a single anisotropic gap nature. In addition, considering its nearly flat top valence band which is favorable for high temperature superconductivity, we also explore the superconducting properties of hole-doped monolayer arsenene under different strains. the unstrained monolayer arsenene superconducts at Tc = 0.22 K with 0.1 hole/cell doping. By applying 3% biaxial strain, Tc can be lifted up strikingly to 6.69 K due to a strong Fermi nesting of the nearly flat band. Then Tc decreases slowly with strain. Our findings provide another insight to realize 2D superconductivity and suggest that the strain is crucial to further enhance the transition temperature.

Characterization of point defects in monolayer arsenene

Topological defects that are inevitably found in 2D materials can dramatically affect their properties. Using density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) method, the structural, thermodynamic, electronic and magnetic properties of six types of typical point defects in arsenene, i.e. the Stone-Wales defect, single and double vacancies and adatoms, were systemically studied. It was found that these defects were all more easily generated in arsenene with lower formation energies than those with graphene and silicene. Stone-Wales defects can be transformed from pristine arsenene by overcoming a barrier of 2.19 eV and single vacancy defects tend to coalesce into double vacancy defects by diffusion. However, a type of adatom defect does not exhibit kinetic stability at room temperature. In addition, SV defects and another type of adatom defect can remarkably affect the electronic and magnetic properties of arsenene, e.g. they can introduce localized states near the Fermi level, as well as a strongly local magnetic moment due to dangling bond and unpaired electron. Furthermore, the simulated scanning tunneling microscopy (STM) and Raman spectroscopy were computed and the types of point defects can be fully characterized by correlating the STM images and Raman spectra to the defective atomistic structures. The results provide significant insights to the effect of defects in arsenene for potential applications, as well as identifications of two helpful tools (STM and Raman spectroscopy) to distinguish the type of defects in arsenene for future experiments.

Ab Initio Study of Magnetism in Nonmetal Adsorption on Arsenene Monolayer

The structural, electronic, and magnetic properties of adsorbed arsenene monolayer with a series of nonmetal atoms, including B, C, F, N, and O, are systematically investigated using first-principles calculations. Nonmagnetic behavior shows in the B-, F-, N-, and O-adsorbed systems. The magnetism has been observed in the case of C, which originated from the 2p electrons of C and its neighboring As 4p states. Meanwhile, these nonmagnetic elements can induce impurity channels around Fermi level, which reduce band gap of the systems. It implies that the B-, F-, N-, and O-adsorbed arsenene tune into narrow gap semiconductors without magnetic character. The X-adsorbed (X = B, C, F, N, and O) arsenene systems are promising candidates for spintronic devices in the future.

Modulating the electronic and optical properties of monolayer arsenene phases by organic molecular doping

Recently, arsenene monolayer structure of the arsenic with two phases has displayed semiconducting behavior. We have systematically investigated the electronic and optical properties of single-layer arsenene with two types of functionalized organic molecules; an electrophilic molecule [tetracyanoquinodimethane (TCNQ)] and a nucleophilic molecule [tetrathiafulvalene (TTF)], as an electron acceptor and electron donor, respectively. The interfacial charge transfer between the arsenene monolayer and TCNQ/TTF molecules extensively reduces the band gap of arsenene and accordingly resulted in a p- or n-type semiconducting behavior, respectively. We have also performed the interfacial charge transfer from organic molecules to monolayer arsenene and vice versa. The interfacial surface molecular modification has established an efficient way to develop the light harvesting of arsenene in different polarization directions. Our theoretical investigation suggests that such n- and p-type arsenene semiconductors would broaden the applications in the field of nanoelectronic and optoelectronic devices such as photodiodes and it is also useful for constructing functional electronic systems.

Magnetic coupling in nonmagnetic metal adsorption on arsenene monolayer: Ab initio study

The structural, electronic and magnetic properties of adsorbed arsenene monolayer with a series of nonmagnetic metal atoms, including Al, Ga, Li, Mg, and Na, are systematically investigated using first-principles calculations. From our calculations, nonmagnetic states appear in the cases of Li, Mg, and Na. The magnetism has been observed for Al and Ga adatoms. Then, we study the magnetic interaction between the moments induced by Al and Ga adatoms. It is found that a p–d exchange-like p-p hybridization results in the ferromagnetic (FM) state. However, when the distance of Ga-Ga or Al-Al is increased, it is found out that the FM interaction has been extremely depressed. This phenomenon can be explained by a simple Heisenberg model. The X-adsorbed (X= Al and Ga) arsenene systems are promising candidates for spintronic devices in the future.

Electrical Contacts in Monolayer Arsenene Devices.

Arsenene, arsenic analogue of graphene, as an emerging member of two-dimensional semiconductors (2DSCs), is quite promising in next-generation electronic and optoelectronic applications. The metal electrical contacts play a vital role in the charge transport and photoresponse processes of nanoscale 2DSC devices and even can mask the intrinsic properties of 2DSCs. Here, we present a first comprehensive study of the electrical contact properties of monolayer (ML) arsenene with different electrodes by using ab initio electronic calculations and quantum transport simulations. Schottky barrier is always formed with bulk metal contacts owing to the Fermi level pinning (pinning factor S = 0.33), with electron Schottky barrier height (SBH) of 0.12, 0.21, 0.25, 0.35, and 0.50 eV for Sc, Ti, Ag, Cu, and Au contacts and hole SBH of 0.75 and 0.78 eV for Pd and Pt contacts, respectively. However, by contact with 2D graphene, the Fermi level pinning effect can be reduced due to the suppression of metal-induced gap states. Remarkably, a barrier free hole injection is realized in ML arsenene device with graphene-Pt hybrid electrode, suggestive of a high device performance in such a ML arsenene device. Our study provides a theoretical foundation for the selection of favorable electrodes in future ML arsenene devices.

Electronic and magnetic properties of Ga, Ge, P and Sb doped monolayer arsenene

In this paper, the structural, electronic, and magnetic properties of Ga, Ge, P and Sb doped monolayer arsenene have been systematically investigated by first-principles calculations based on density functional theory. The properties of monolayer arsenene can be effectively tuned by substitutional doping. Especially, the dopant Ga could lead to an indirect-to-direct bandgap transition and doping a Ge atom could exhibit dilute magnetic semiconductor property. In addition, the second Ge atom slightly prefers to occupy the next nearest-neighbor site of As atom to form the complex substituted defect (GeAs - As - GeAs) in As30Ge2 system and is found to be anti-ferromagnetic coupling. The diverse electronic and magnetic properties highlight the potential applications of monolayer arsenene in electronics, optoelectronics and spintronics.

Many-body Effect, Carrier Mobility, and Device Performance of Hexagonal Arsenene and Antimonene

Two-dimensional (2D) semiconductors are very promising channel materials in next-generation field effect transistors (FETs) due to the enhanced gate electrostatics and smooth surface. Two new 2D materials, arsenene and antimonene (As and Sb analogues of graphene), have been fabricated very recently. Here, we provide the first investigation of the many-body effect, carrier mobility, and device performance of monolayer (ML) hexagonal arsenene and antimonene based on accurate ab initio methods. The quasi-particle band gaps of ML arsenene and antimonene by using the GW approximation are 2.47 and 2.38 eV, respectively. The optical band gaps of ML arsenene and antimonene from the GW-Bethe–Salpeter equation are 1.6 and 1.5 eV, with exciton binding energies of 0.9 and 0.8 eV, respectively. The carrier mobility is found to be considerably low in ML arsenene (21/66 cm2/V·s for electron/hole) and moderate in ML antimonene (150/510 cm2/V·s for electron/hole). In terms of the ab initio quantum transport simulations, t...

Arsenene as a promising candidate for NO and NO2 sensor: A first-principles study

Based on first-principles calculations, we have studied the adsorption of CO, CO2, N2, NH3, NO and NO2 molecules on the pristine arsenene monolayer. These gas molecules are held by an interaction that is intermediate between the physisorbed and chemisorbed states. Furthermore, the adsorption of NO and NO2 can produce a noticeable modifications of the density of states near the Fermi level. Interestingly, only the adsorption of NO and NO2 can lead to a magnetic moment of 1 μB. Therefore, our results can provide a theoretical basis for the potential applications of arsenene monolayer in gas sensing with electrical and magnetic methods.

First‐principle calculations of optical properties of monolayer arsenene and antimonene allotropes

Recently a stable monolayer of antimony in buckled honeycomb structure called antimonene was successfully grown on 3D topological insulator Bi2Te3 and Sb2Te3, which displays novel semiconducting properties. By first‐principle calculations, we systematically investigate the electronic and optical properties of α‐ and β‐allotropes of monolayer arsenene/antimonene. The obtained electronic structures reveal that the direct band gap of α‐arsenene/antimonene is much smaller than the indirect band gap of their β‐counterpart, respectively. Significant absorption is observed in α‐antimonene, which can be used as a broad saturable absorber. For β‐arsenene/antimonene, the reflectivity is low and the absorption is negligible in the visible region when the polarization along the out‐plane direction, indicating that β‐arsenene/antimonene are polarizationally transparent materials.image

Electronic and Optical Properties of Arsenene Under Uniaxial Strain

The electronic and optical properties of strained monolayer arsenene were calculated based on first-principle density functional theory. Our theoretical calculations demonstrated that monolayer arsenene was transformed from indirect to direct band gap semiconductor by inducing uniaxial tensile strain along armchair and zigzag directions. Compared to the biaxial tensile strain of 0.04, this transformation occurred at the strain of 0.06 and 0.10 along armchair and zigzag direction, respectively. Spin–orbital coupling is available to tune the bandgaps. The spin–orbit interaction opens a 0.2 eV bandgap in the Γ-point on the unstrained monolayer arsenene. The absorption properties were calculated and a clear red shift was observed with the increasing strain.

Optical Identification of Topological Defect Types in Monolayer Arsenene by First-Principles Calculation

Recent theoretical research has demonstrated that a new two-dimensional material, the monolayer of gray arsenic (arsenene), can respond to the blue and ultraviolet light leading to possible optoelectronic applications. However, some topological defects often affect various properties of arsenene. Here we theoretically investigate the arsenene with monovacancy (MV), divacancy (DV), and Stone–Wales (SW) defects. Three kinds of MVs are identified and the reconstructed structures of DV and SW defects are confirmed. The dynamical stability, rearrangement, and migration for these defects are investigated in detail. Optical spectral calculations indicate that the MVs enhance optical transitions in the forbidden bands of arsenene and two new characteristic peaks appear in the dielectric and absorption spectra. However, there is only one new peak in the spectrum induced by DV and SW defects. Calculations of band structures indicate that the MV induces two defect bands in the forbidden bands of pristine arsenene, w...

Theoretical insight into structure stability, elastic property and carrier mobility of monolayer arsenene under biaxial strains

Through theoretical calculations, we investigate the structure stability, elastic property and carrier mobility of Arsenene. Using phonon spectra and elastic constant, we verify the dynamic stability and mechanical stability of Arsenene. Based on the stable structure, we study the elastic property and carrier mobility. The bulk modulus, shear modulus, Young's modulus, Poisson's ratio are calculated. Finally, the Shear anisotropy, Vicker hardness, Debye temperature, melting point and thermal conductivity have been predicted. According to deformation potential theory, under different strain and temperature, the electron mobility and relaxation time are also calculated.

Performance of arsenene and antimonene double-gate MOSFETs from first principles.

In the race towards high-performance ultra-scaled devices, two-dimensional materials offer an alternative paradigm thanks to their atomic thickness suppressing short-channel effects. It is thus urgent to study the most promising candidates in realistic configurations, and here we present detailed multiscale simulations of field-effect transistors based on arsenene and antimonene monolayers as channels. The accuracy of first-principles approaches in describing electronic properties is combined with the efficiency of tight-binding Hamiltonians based on maximally localized Wannier functions to compute the transport properties of the devices. These simulations provide for the first time estimates on the upper limits for the electron and hole mobilities in the Takagi's approximation, including spin–orbit and multi-valley effects, and demonstrate that ultra-scaled devices in the sub-10-nm scale show a performance that is compliant with industry requirements.

Anisotropic Thermoelectric Response in Two-Dimensional Puckered Structures

Two-dimensional semiconductor materials with puckered structure offer a novel playground to implement nanoscale thermoelectric, electronic, and optoelectronic devices with improved functionality. Using a combination of approaches to compute the electronic and phonon band structures with Green’s function based transport techniques, we address the thermoelectric performance of phosphorene, arsenene, and SnS monolayers. In particular, we study the influence of anisotropy in the electronic and phononic transport properties and its impact on the thermoelectric figure of merit ZT. Our results show no strong electronic anisotropy, but a strong thermal one, the effect being most pronounced in the case of SnS monolayers. This material also displays the largest figure of merit at room temperature for both transport directions, zigzag (ZT ∼ 0.95) and armchair (ZT ∼ 1.6), thus hinting at the high potential of these new materials in thermoelectric applications.

Transition metal doped arsenene: A first-principles study

Using first-principles calculations, we investigate the structural, electronic, and magnetic properties of 3d transition metal (TM) atoms substitutional doping of an arsenene monolayer. Based on the binding energy, the TM-substituted arsenene systems were found to be robust. Magnetic states were obtained for Ti, V, Cr, Mn and Fe doping. More importantly, a half-metallic state resulted from Ti and Mn doping, while the spin-polarized semiconducting state occurred with V, Cr and Fe doping. Our studies demonstrated the potential applications of TM-substituted arsenene for spintronics and magnetic storage devices.

Strain engineering band gap, effective mass and anisotropic Dirac-like cone in monolayer arsenene

The electronic properties of two-dimensional puckered arsenene have been investigated using first-principles calculations. The effective mass of electrons exhibits highly anisotropic dispersion in intrinsic puckered arsenene. Futhermore, we find that out-of-plane strain is effective in tuning the band gap, as the material undergoes the transition into a metal from an indirect gap semiconductor. Remarkably, we observe the emergence of Dirac-like cone with in-plane strain. Strain modulates not only the band gap of monolayer arsenene, but also the effective mass. Our results present possibilities for engineering the electronic properties of two-dimensional puckered arsenene and pave a way for tuning carrier mobility of future electronic devices.

Controllable band structure and topological phase transition in two-dimensional hydrogenated arsenene.

Discovery of two-dimensional (2D) topological insulator such as group-V films initiates challenges in exploring exotic quantum states in low dimensions. Here, we perform first-principles calculations to study the geometric and electronic properties in 2D arsenene monolayer with hydrogenation (HAsH). We predict a new σ-type Dirac cone related to the px,y orbitals of As atoms in HAsH, dependent on in-plane tensile strain. Noticeably, the spin-orbit coupling (SOC) opens a quantum spin Hall (QSH) gap of 193 meV at the Dirac cone. A single pair of topologically protected helical edge states is established for the edges, and its QSH phase is confirmed with topological invariant Z2 = 1. We also propose a 2D quantum well (QW) encapsulating HAsH with the h-BN sheet on each side, which harbors a nontrivial QSH state with the Dirac cone lying within the band gap of cladding BN substrate. These findings provide a promising innovative platform for QSH device design and fabrication operating at room temperature.

Tunable quantum spin Hall effect via strain in two-dimensional arsenene monolayer

The search for a new quantum spin Hall (QSH) phase and effective manipulation of its edge states are very important for both fundamental sciences and practical applications. Here, we use first-principles calculations to study the strain-driven topological phase transition of two-dimensional (2D) arsenene monolayer. We find that the band gap of arsenene decreases with increasing strain and changes from indirect to direct, and then the s-p band inversion takes place at the Г point as the tensile strain is larger than 11.14%, which leads to a nontrivially topological state. A single pair of topologically protected helical edge states is established for the edge of arsenene, and their QSH states are confirmed with the nontrivial topological invariant Z2 = 1. We also propose high-dielectric BN as an ideal substrate for the experimental synthesis of arsenene, maintaining its nontrivial topology. These findings provide a promising candidate platform for topological phenomena and new quantum devices operating at nanoelectronics.