Alternating spin splitting of electronic and magnon bands in two-dimensional altermagnetic materials

Unconventional antiferromagnetism dubbed as altermagnetism was first discovered in rutile structured magnets,which is featured by spin splitting even without the spin–orbital coupling effect.This interesting phenomenon has been discovered in more altermagnetic materials.In this work,we explore two-dimensional altermagnetic materials by studying two series of two-dimensional magnets,including MF4 with M covering all 3d and 4d transition metal elements,as well as TS2 with T=V,Cr,Mn,Fe.Through the magnetic symmetry operation of RuF4 and MnS2,it is verified that breaking the time inversion is a necessary condition for spin splitting.Based on symmetry analysis and first-principles calculations,we find that the electronic bands and magnon dispersion experience alternating spin splitting along the same path.This work paves the way for exploring altermagnetism in two-dimensional materials.

Understanding the hydrogen evolution reaction activity of doped single-atom catalysts on two-dimensional GaPS_(4) by DFT and machine learning

As a zero-carbon fuel,hydrogen can be produced via electrochemical water splitting using clean electric energy by the hydrogen evolution reaction(HER)process.The ultimate goal of HER catalyst is to replace the expensive Pt metal benchmark with a cheap one with equivalent activities.In this work,we investigated the possibility of HER process on single-atom catalysts(SACs)doped on two-dimensional(2D)GaPS_(4)materials,which have a large intrinsic band gap that can be regulated by doping and tensile strain.Based on the machine learning regression analysis,we can expand the prediction of HER performance to more catalysts without expensive DFT calculation.The electron affinity and first ionization energy are the two most important descriptors related to the HER behavior.Furthermore,constrain molecular dynamics with solvation models and constant potentials were applied to understand the dynamics barrier of HER process of Pt SAC on GaPS_(4)materials.These findings not only provide important insights into the catalytic properties of single-atom catalysts on GaPS_(4)2D materials,but also provides theoretical guidance paradigm for exploration of new catalysts.

High-temperature ferromagnetism and strongπ-conjugation feature in two-dimensional manganese tetranitride

Two-dimensional(2D)magnetic materials have attracted tremendous research interest because of the promising application in the next-generation microelectronic devices.Here,by the first-principles calculations,we propose a twodimensional ferromagnetic material with high Curie temperature,manganese tetranitride MnN4monolayer,which is a square-planar lattice made up of only one layer of atoms.The structure is demonstrated to be stable by the phonon spectra and the molecular dynamic simulations,and the stability is ascribed to theπ–d conjugation betweenπorbital of N=N bond and d orbital of Mn.More interestingly,the MnN_(4)monolayer displays robust 2D ferromagnetism,which originates from the strong exchange couplings between Mn atoms due to theπ–d conjugation.The high critical temperature of 247 K is determined by solving the Heisenberg model using the Monte Carlo method.

Li_(2)NiSe_(2):A new-type intrinsic two-dimensional ferromagnetic semiconductor above 200 K

By using first-principles electronic structure calculations,we propose a two-dimensional ferromagnetic semiconductor Li_(2)NiSe_(2)with a Curie temperature above 200 K.The structure of monolayer Li_(2)NiSe_(2)is dynamically stable,which is derived from the synthesized prototype compound Li_(2)Ni O_(2)and can be denoted as Li-decorated 1T-type NiSe_(2).The Ni–Se–Ni ferromagnetic superexchange dominates the magnetic couplings between the Ni atoms,which can be understood in the frame of the Goodenough–Kanamori–Anderson(GKA)rules.Our systematic study of monolayer Li_(2)NiSe_(2)enables its promising applications in spintronics and suggests a new choice to design two-dimensional ferromagnetic semiconductors.

Magnetic and electronic properties of bulk and two-dimensional FeBi_(2)Te_(4):A first-principles study

Layered magnetic materials,such as MnBi_(2)Te_(4),have drawn much attention owing to their potential for realizing twodimensional(2D)magnetism and possible topological states.Recently,FeBi_(2)Te_(4),which is isostructural to MnBi_(2)Te_(4),has been synthesized in experiments,but its detailed magnetic ordering and band topology have not been clearly understood yet.Here,based on first-principles calculations,we investigate the magnetic and electronic properties of FeBi_(2)Te_(4)in bulk and 2D forms.We show that different from MnBi_(2)Te_(4),the magnetic ground states of bulk,single-layer,and bilayer FeBi_(2)Te_(4)all favor a 120°noncollinear antiferromagnetic ordering,and they are topologically trivial narrow-gap semiconductors.For the bilayer case,we find that a quantum anomalous Hall effect with a unit Chern number is realized in the ferromagnetic state,which may be achieved in experiment by an external magnetic field or by magnetic proximity coupling.Our work clarifies the physical properties of the new material system of FeBi_(2)Te_(4)and reveals it as a potential platform for studying magnetic frustration down to 2D limit as well as quantum anomalous Hall effect.

A family of flexible two-dimensional semiconductors:MgMX2Y6(M=Ti/Zr/Hf;X=Si/Ge;Y=S/Se/Te)

Inspired by the recently predicted 2D MX_(2)Y_(6)(M=metal element;X=Si/Ge/Sn;Y=S/Se/Te),we explore the possible applications of alkaline earth metal(using magnesium as example)in this family based on the idea of element replacement and valence electron balance.Herein,we report a new family of 2D quaternary compounds,namely MgMX_(2)Y_(6)(M=Ti/Zr/Hf;X=Si/Ge;Y=S/Se/Te)monolayers,with superior kinetic,thermodynamic and mechanical stability.In addition,our results indicate that MgMX_(2)Y_(6)monolayers are all indirect band gap semiconductors with band gap values ranging from 0.870 to 2.500 eV.Moreover,the band edges and optical properties of 2D MgMX_(2)Y_(6)are suitable for constructing multifunctional optoelectronic devices.Furthermore,for comparison,the mechanical,electronic and optical properties of In_(2)X_(2)Y_(6)monolayers have been discussed in detail.The success of introducing Mg into the 2D MX_(2)Y_(6)family indicates that more potential materials,such as Caand Sr-based 2D MX_(2)Y_(6)monolayers,may be discovered in the future.Therefore,this work not only broadens the existing family of 2D semiconductors,but it also provides beneficial results for the future.

Screening of low-friction two-dimensional materials from highthroughput calculations using lubricating figure of merit

Two-dimensional materials are excellent lubricants with inherent advantages.However,superlubricity has been reported for only a few of these materials.Unfortunately,other promising two-dimentional(2D)materials with different physical properties cannot be discovered or applied in production;thus,energy consumption can be greatly reduced.Here,we carry out high-throughput calculations for 1,4752D materials and screen for low-friction materials.To set a standard,we propose,for the first time,a geometry-independent lubricating figure of merit based on the conditions for stick-slip transition and our theory of Moiréfriction.For the efficient calculation of this figure of merit,an innovative approach was developed based on an improved registry index model.Through calculations,340 materials were found to have a figure of merit lower than 10−3.Eventually,a small set of 21 materials with a figure of merit lower than 10−4 were screened out.These materials can provide diverse choices for various applications.In addition,the efficient computational approach demonstrated in this work can be used to study other stacking-dependent properties.

Core level excitation spectra of La and Mn ions in LaMnO3

Manganese-based perovskite is popular for research on ferromagnetic materials,and its spectroscopic studies are essential for understanding its electronic structure,dielectric,electrical,and magnetic properties.In this paper,the M-edge spectra of La ions and the M-edge,L-edge,and K-edge spectra of Mn ions in LaMnO3 are calculated by considering both the free-ion multiplet calculation and the crystal field effects.We analyze spectral shapes,identify peak origins,and estimate the oxidation states of La and Mn ions in LaMnO3 theoretically.It is concluded that La ions in LaMnO3 predominantly exist in the trivalent state,while Mn ions exist primarily in the trivalent state with a minor presence of tetravalent ions.Furthermore,the calculated spectra are in better conformity with the experimental spectra when the proportion of Mn3+is 90%and Mn4+is 10%.This article enhances our comprehension of the oxidation states of La and Mn within the crystal and also provides a valuable guidance for spectroscopic investigations of other manganates.

First-principles investigation of the significant anisotropy and ultrahigh thermoelectric efficiency of a novel two-dimensional Ga_(2)I_(2)S_(2) at room temperature

Two-dimensional(2D)thermoelectric(TE)materials have been widely developed;however,some 2D materials exhibit isotropic phonon,electron transport properties,and poor TE performance,which limit their application scope.Thus,exploring excellent anisotropic and ultrahigh-performance TE materials are very warranted.Herein,we first investigate the phonon thermal and TE properties of a novel 2D-connectivity ternary compound named Ga2I2S2.This paper comprehensively studies the phonon dispersion,phonon anharmonicity,lattice thermal conductivity,electronic structure,carrier mobility,Seebeck coefficient,electrical conductivity,and the dimensionless figure of merit(ZT)versus carrier concentration for 2D Ga_(2)I_(2)S_(2).We conclude that the in-plane lattice thermal conductivities of Ga_(2)I_(2)S_(2) at room temperature(300 K)are found to be 1.55 W mK^(−1) in the X-axis direction(xx-direction)and 3.82 W mK^(−1)in the Y-axis direction(yy-direction),which means its anisotropy ratio reaches 1.46.Simultaneously,the TE performance of p-type and n-type doping 2D Ga2I2S2 also shows significant anisotropy,giving rise to the ZT peak values of p-type doping in xx-and yy-directions being 0.81 and 1.99,respectively,and those of n-type doping reach ultrahigh values of 7.12 and 2.89 at 300 K,which are obviously higher than the reported values for p-type and n-type doping ternary compound Sn2BiX(ZT∼1.70 and∼2.45 at 300 K)(2020 Nano Energy 67104283).This work demonstrates that 2D Ga_(2)I_(2)S_(2) has high anisotropic TE conversion efficiency and can also be used as a new potential room-temperature TE material.

Net-C18:A Predicted Two-Dimensional Planar Carbon Allotrope and Potential for an Anode in Lithium-Ion Battery

Net-C18,a predicted two-dimensional(2D)graphene-like carbon allotrope,is investigated via first-principles calculations.Its space group is Pmmm.There are 18 carbon atoms per cell.Net-C18 has five-,six-,and eight-membered rings.Net-C18 may be formed by adding even pairs of carbon atoms on the top of hexagons to reconstruct new five-and eight-membered rings,extending the strategy of Haeckelite.Compared to that of graphene(-9.28 e V atom^(-1)),the total energy of net-C18(-9.15 e V atom^(-1))is only 0.13 e V atom^(-1)higher,revealing that net-C18 is energetically metastable.The calculations of phonon and ab initio molecular dynamics(AIMD)demonstrate dynamical and thermal stability of net-C18.The independent elastic constants of net-C18 meet the criterial for the mechanical stability of 2D structure.Its in-plane stiffness along x or y axis is comparably large.The AIMD results reveal that net-C18 has good thermal stability at 1500 K.The band structure also demonstrates that it is metallic.Furthermore,the diffusion of Li atoms on net-C18 has a low energy barrier(0.32 e V),and net-C18 has a low open-circuit voltage(0.024 V)and a high theoretical specific capacity(403 m Ah g^(-1)).Thus,net-C18 may provide high-temperature resistant,flexible electrode in electronics and a promising metallic anode in lithium-ion battery.The proposed formation of net-C18 may open a new pattern defect for the designs of new carbon allotropes.

High-throughput computational material screening of the cycloalkane-based two-dimensional Dion–Jacobson halide perovskites for optoelectronics

Two-dimensional(2D) layered perovskites have emerged as potential alternates to traditional three-dimensional(3D)analogs to solve the stability issue of perovskite solar cells. In recent years, many efforts have been spent on manipulating the interlayer organic spacing cation to improve the photovoltaic properties of Dion–Jacobson(DJ) perovskites. In this work, a serious of cycloalkane(CA) molecules were selected as the organic spacing cation in 2D DJ perovskites, which can widely manipulate the optoelectronic properties of the DJ perovskites. The underlying relationship between the CA interlayer molecules and the crystal structures, thermodynamic stabilities, and electronic properties of 58 DJ perovskites has been investigated by using automatic high-throughput workflow cooperated with density-functional(DFT) calculations.We found that these CA-based DJ perovskites are all thermodynamic stable. The sizes of the cycloalkane molecules can influence the degree of inorganic framework distortion and further tune the bandgaps with a wide range of 0.9–2.1 eV.These findings indicate the cycloalkane molecules are suitable as spacing cation in 2D DJ perovskites and provide a useful guidance in designing novel 2D DJ perovskites for optoelectronic applications.

Two-dimensional titanium carbonitride MXene as a highly efficient electrocatalyst for hydrogen evolution reaction

In this paper,we report,for the first time,on the electrochemical catalytic activity of 2D titanium carbonitride MXene for hydrogen evolution reaction(HER).According to our study,2D titanium carbonitride exhibited much higher electrocatalytic activity than its carbide analogues,achieving an onset overpotential of 53 mV and Tafel slope of 86 mV dec^(-1),superior to the titanium carbide with onset overpotential of 649 mV and Tafel slope of 303 mV dec^(-1).The obtained onset overpotential for 2D titanium carbonitride is lower than those of all the reported transition metal carbides MXene catalysts without additives,so far.Density functional theory calculations were conducted to further understand the electrochemical performance.The calculation results show that a greater number of occupied states are active for Ti_(3)CNO_(2),revealing free energy for the adsorption of atomic hydrogen closer to 0 than that of Ti_(3)C_(2)O_(2).Both experimental and calculation studies demonstrate the excellent electrocatalytic behavior of titanium carbonitride.The investigation of 2D titanium carbonitride opens up a promising paradigm for the conscious design of high-performance non-precious metal catalyst for hydrogen generation.

An antiferromagnetic two-dimensional material: Chromium diiodides monolayer

The two-dimensional(2D)ferromagnetic materials and the related van der Waals homostructures have attracted considerable interest,while the 2D antiferromagnetic material has not yet been reported.Based on first-principles calculations,we investigate both electronic structures and magnetic orderings of bulk and monolayer of chromium diiodides(CrI2).We demonstrate a counter-intuitive fact that the ground state of the free-standing monolayer of CrI2 is antiferromagnetic though the bulk possesses macroscopic ferromagnetic ordering.The interlayer interaction remains antiferromagnetic up to few-layer scenarios.The unique feature of CrI2 makes it an ideal workbench to investigate the relation between magnetic couplings and interlayer van der Waals interactions,and may offer an opportunity to 2D antiferromagnetic spintronic devices.

First-principles study on improvement of two-dimensional hole gas concentration and confinement in AlN/GaN superlattices

Using first-principles calculations based on density functional theory,we have systematically studied the influence of in-plane lattice constant and thickness of slabs on the concentration and distribution of two-dimensional hole gas(2 DHG)in AlN/GaN superlattices.We show that the increase of in-plane lattice constant would increase the concentration of 2 DHG at interfaces and decrease the valence band offset,which may lead to a leak of current.Increasing the thickness of AlN and/or decreasing the thickness of GaN would remarkably strengthen the internal field in GaN layer,resulting in better confinement of 2 DHG at AlN/GaN interfaces.Therefore,a moderate larger in-plane lattice constant and thicker AlN layer could improve the concentration and confinement of 2 DHG at AlN/GaN interfaces.Our study could serve as a guide to control the properties of 2 DHG at Ⅲ-nitride interfaces and help to optimize the performance of p-type nitride-based devices.

Giant Rashba-like spin-orbit splitting with distinct spin texture in two-dimensional heterostructures

Based on first-principles density functional theory calculation,we discover a novel form of spin-orbit(SO)splitting in two-dimensional(2D)heterostructures composed of a single Bi(111)bilayer stacking with a 2D semiconducting In_(2)Se_(2) or a 2D ferroelectricα-In_(2)Se_(3) layer.Such SO splitting has a Rashba-like but distinct spin texture in the valence band around the maximum,where the chirality of the spin texture reverses within the upper spin-split branch,in contrast to the conventional Rashba systems where the upper branch and lower branch have opposite chirality solely in the region below the band crossing point.The ferroelectric nature ofα-In_(2)Se_(3) further enables the tuning of the spin texture upon the reversal of the electric polarization with the application of an external electric field.Detailed analysis based on a tight-binding model reveals that such SO splitting texture results from the interplay of complex orbital characters and substrate interaction.This finding enriches the diversity of SO splitting systems and is also expected to promise for spintronic applications.

Temperature-induced phase transition of two-dimensional semiconductor GaTe

GaTe is a two-dimensional Ⅲ-Ⅵ semiconductor with suitable direct bandgap of~1.65 eV and high photoresponsivity,which makes it a promising candidate for optoelectronic applications.GaTe exists in two crystalline phases:monoclinic(m-GaTe,with space group C2/m) and hexagonal(h-GaTe,with space group P63/mmc).The phase transition between the two phases was reported under temperature-varying conditions,such as annealing,laser irradiation,etc.The explicit phase transition temperature and energy barrier during the temperature-induced phase transition have not been explored.In this work,we present a comprehensive study of the phase transition process by using first-principles energetic and phonon calculations within the quasi-harmonic approximation framework.We predicted that the phase transition from h-GaTe to m-GaTe occurs at the temperature decreasing to 261 K.This is in qualitative agreement with the experimental observations.It is a two-step transition process with energy barriers 199 meV and 288 meV,respectively.The relatively high energy barriers demonstrate the irreversible nature of the phase transition.The electronic and phonon properties of the two phases were further investigated by comparison with available experimental and theoretical results.Our results provide insightful understanding on the process of temperature-induced phase transition of GaTe.

First-principles investigation of chemical modification on two-dimensional iron-phthalocyanine sheet

Successful synthesis of single iron-phthalocyanie （FePc） framework layer on substrate and its transferrable properties open the door for decorating the separately distributed transition metals for exploring the diverse properties. We have studied the effects of chemical modification on two-dimensional FePc organometallic framework with density functional theory. For simplicity, the non-metal atoms with variant valence electrons are used as prototypes to estimate the effects ＆ore chemical modifications with different functional groups. The thermo-stabilities of the non-metal atom decorated complex sheet materials have been estimated by the first-principles constant energy molecular dynamic simulations. Upon the non- metal atom adsorption, the magnetic moment could be changed from 2 ~tB to 0, 1, 2, and 3 ~tB per unit cell for the case of tetra-, penta-, hexa-, and hepta-valent non-metal modifications, respectively, showing interesting promise to tailor its magnetic properties for potential applications.

Mo_(3)(C_(6)X_(6))_(2)(X=NH,S,O)monolayers:two-dimensional conductive metal-organic frameworks as effective electrocatalysts for the nitrogen reduction reaction

As a constituent element of amino acids,nitrogen plays an important role in nourishing plants,animals and other forms of life.Although the atmosphere is rich in nitrogen gas(N_(2)),the highly inert N≡N bond makes it difficult for most organisms to directly utilize N_(2).The supply of nitrogen in the biological chain mainly depends on the slow conversion of N_(2) to ammonia(NH3)by biological nitrogen fixation[1].

Two-dimensional hexagonal Zn3Si2 monolayer:Dirac cone material and Dirac half-metallic manipulation

The fascinating Dirac cone in honeycomb graphene,which underlies many unique electronic properties,has inspired the vast endeavors on pursuing new two-dimensional(2D)Dirac materials.Based on the density functional theory method,a 2D material Zn3Si2 of honeycomb transition-metal silicide with intrinsic Dirac cones has been predicted.The Zn3Si2 monolayer is dynamically and thermodynamically stable under ambient conditions.Importantly,the Zn3Si2 monolayer is a room-temperature 2D Dirac material with a spin-orbit coupling energy gap of 1.2 meV,which has an intrinsic Dirac cone arising from the special hexagonal lattice structure.Hole doping leads to the spin polarization of the electron,which results in a Dirac half-metal feature with single-spin Dirac fermion.This novel stable 2D transition-metal-silicon-framework material holds promises for electronic device applications in spintronics.

预制模壳填芯混凝土悬臂盖梁承载力分析

盖梁的轻量化发展是实现全预制桥梁的必然要求。基于已有的预制模壳填芯混凝土悬臂盖梁静力试验,采用有限元软件ABAQUS对试件PRC1进行数值分析,有限元计算结果和试验结果吻合较好,验证了有限元模型的可靠性。通过修改已验证的有限元模型参数,进一步分析外壳混凝土强度、纵筋配筋率和交界面接触设置对预制模壳填芯混凝土悬臂盖梁力学性能的影响。基于钢筋混凝土一般构件的承载力计算方法建立试件的理论计算公式,并对提出的计算公式进行验证。研究结果表明:当外壳材料为普通混凝土时,混凝土强度等级从C35增加到C60,峰值承载力仅提高1%,而当外壳材料为超高性能混凝土(UHPC)时,峰值承载力相较C35提高了22%。纵筋配筋率与峰值承载力呈线性增长趋势,当顶部第1排纵筋直径从14 mm增加到22 mm时,峰值承载力提高了34%。交界面接触设置为绑定约束比面面接触的峰值承载力更接近试验值,且后者是相对保守的。基于钢筋混凝土一般构件建立的承载力计算方法所计算结果与试验结果和有限元分析结果吻合较好。