Carrier and magnetism engineering for monolayer SnS2 by high throughput first-principles calculations

Two-dimensional (2D) semiconducting tin disulfide (SnS₂) has been widely used for optoelectronic applications. To functionalize SnS₂ for extending its application, we investigate the stability, electronic and magnetic properties of substitutional doping by high throughput first-principles calculations. There are a lot of elements that can be doped in monolayer SnS₂. Nonmetal in group A can introduce p-type and n-type carriers, while most metals in group A can only lead to p-type doping. Not only 3d, but also 4d and 5d transition metals in groups VB to VⅢB9 can introduce magnetism in SnS₂, which is potentially applicable for spintronics. This study provides a comprehensive view of functionalization of SnS₂ by substitutional doping, which will guide further experimental realization.     

Strain-induced ferroelectric phase transitions in incipient ferroelectric rutile TiO2

Uniaxial strain induced ferroelectric phase transitions in rutile TiO₂ are investigated by first-principles calculations. The calculated results show that the in-plane tensile strain induces rutile TiO₂, paraelectric phase with P_4-2/mnm (D_4h) space group, to a ferroelectric phase with P_m (C_s) space group,driven by the softening behaviour of the E_u1 mode. In addition, the out-of-plane tensile strain, vertical to the ab plane, leads to a ferroelectric phase with P_42nm (C_4v) space group, driven by the softening behaviour of the A_2u mode. The critical tensile strains are 3.7% in-plane and 4.0% out-of-plane, respectively. In addition, the in-plane compression strain, which has the same structure variation as out-of-plane tensile strain due to Poisson effect, leads the paraelectric rutile TiO₂ to a paraelectric phase with P_nnm (D_2h) space group driven by the softening behaviour of the B_1g mode. These results indicate that the sequence ferroelectric (or paraelectric) phase depends on the strain applied. The origin of ferroelectric stabilization in rutile TiO₂ is also discussed briefly in terms of strain induced Born effective charge transfer.     

Role of vacancy-type defects in magnetism of GaMnN

Role of vacancy-type(N vacancy(VN) and Ga vacancy(VGa)) defects in magnetism of GaMnN is investigated by first-principle calculation.Theoretical results show that both the VNand VGainfluence the ferromagnetic state of a system.The VNcan induce antiferromagnetic state and the VGaindirectly modify the stability of the ferromagnetic state by depopulating the Mn levels in GaMnN.The transfer of electrons between the vacancy defects and Mn ions results in converting Mn~(3+)(d~4) into Mn~(2+)(d5).The introduced VNand the ferromagnetism become stronger and then gradually weaker with Mn concentration increasing,as well as the coexistence of Mn~(3+)(d~4) and Mn~(2+)(d~5) are found in GaMnN films grown by metal–organic chemical vapor deposition.The analysis suggests that a big proportion of Mn~(3+)changing into Mn~(2+)will reduce the exchange interaction and magnetic correlation of Mn atoms and lead to the reduction of ferromagnetism of material.     

Strain-induced structural and direct-to-indirect band gap transition in ZnO nanotubes

First-principles calculations have been employed to investigate the structural transformation and direct to indirect band gap transition of ZnO nanotubes under uniaxial strain. The results show that armchair and zigzag nanotubes can be transformed to each other via unusual fourfold-coordinated structures under the applied strain. Both the armchair and zigzag nanotubes exhibit direct band gap while the unusual fourfold-coordinated ones display indirect band gap. The origin of such a direct-to-indirect band gap transition is explained based on the analyses of atomic orbital contributions.     

First principles study of the magnetism driven by cation defects in CeO2: the important role of O2p states

The magnetism driven by cation defects in undoped CeO2 bulk and thin films is studied by the density functional theory corrected for on-site Coulomb interactions （DFT＋U） with U = 5 eV for the Ce4f states and U = 7 eV for the O2p states. It is found that the Ce vacancies can induce a magnetic moment of the -4 gB/supercell, which arises mainly from the 2p hole state of the nearest neighbouring O atom （-1μB on per oxygen） to the Ce vacancy. The effect of the methodology is investigated, indicating that U = 7 eV for the O2p state is necessary to obtain the localized O2p hole state in defective ceria with cation vacancies.     

First principles study of the magnetism driven by cation defects in CeO₂:the important role of O2p states

The magnetism driven by cation defects in undoped CeO 2 bulk and thin films is studied by the density functional theory corrected for on-site Coulomb interactions (DFT+U) with U = 5 eV for the Ce4f states and U = 7 eV for the O2p states. It is found that the Ce vacancies can induce a magnetic moment of the ～ 4 μ B /supercell, which arises mainly from the 2p hole state of the nearest neighbouring O atom (～ 1 μ B on per oxygen) to the Ce vacancy. The effect of the methodology is investigated, indicating that U = 7 eV for the O2p state is necessary to obtain the localized O2p hole state in defective ceria with cation vacancies.     

金衬底调控单层二硫化钼电子性能的第一性原理研究

基于密度泛函的第一性原理研究了金衬底对单层二硫化钼电子性能的调控作用. 从结合能、能带结构、电子态密度和差分电荷密度四个方面进行了深入研究. 结合能计算确定了硫原子层在界面的排布方式, 并指出这种吸附结构并不稳定. 能带结构分析证实了金衬底与单层二硫化钼形成肖特基接触, 并出现钉扎效应. 电子态密度分析表明金衬底并没有影响硫原子和钼原子之间的共价键, 而是通过调控单层二硫化钼的电子态密度增加其导电率. 差分电荷密度分析表明单层二硫化钼的导电通道可能在界面处产生. 研究结果可对单层二硫化钼晶体管的建模和实验制备提供指导.     

Modulating the properties of monolayer C_2N: A promising metal-free photocatalyst for water splitting

Photocatalytic water splitting has gained increasing attention, since it utilizes renewable resources, such as water and solar energy, to produce hydrogen. Using the first-principles density functional theory, we investigate the properties of the single layer C_2N which was successfully synthesized. We reveal that monolayer C_2N has a substantial direct band gap of 2.45 eV. To regulate its band gap, four different nonmetal elements(B, O, P, and S) on the cation and anion sites are considered. Among them, B-doped N site is the most effective one, with the lowest formation energy and a band gap of 2.01 eV. P-doped N site is the next, with a band gap of 2.08 eV, though its formation energy is higher. The band alignments with respect to the water redox levels show that, for these two dopings, the thermodynamic criterion for the overall water splitting is satisfied. We therefore predict that B-or P-doped C_2N, with an appropriate band gap and an optimal band-edge position, would be a promising photocatalyst for visible-light water splitting.     

缺陷对单层MoS2电子结构的影响

为了研究缺陷对单层MoS2的电子结构, 本文基于密度泛函理论框架下的第一性原理, 采用数值基组的方法计算了MoS2的Mo位缺陷、S位缺陷的能带结构和态密度.结果发现：Mo位缺陷、S位缺陷的MoS2的能带结构中的价带顶与导带底都在Q点, 为直接带隙材料; 其中Mo位缺陷体的禁带区域都出现5条新能级, S位缺陷体的禁带区域出现了3条新能级; 缺陷体能带结构的能量下降与体系中未成键的电子有关.对于态密度而言, Mo位缺陷体的费米能级处出现了峰值, 表明Mo位缺陷会对其光电性质带来影响.同时分析电荷分布发现, Mo缺陷周围存在着负电荷聚集的现象, S缺陷周围存在正电荷聚集的现象.     

缺陷对单层MoS_2电子结构的影响

为了研究缺陷对单层MoS_2的电子结构,本文基于密度泛函理论框架下的第一性原理,采用数值基组的方法计算了MoS_2的Mo位缺陷、S位缺陷的能带结构和态密度.结果发现:Mo位缺陷、S位缺陷的MoS_2的能带结构中的价带顶与导带底都在Q点,为直接带隙材料;其中Mo位缺陷体的禁带区域都出现5条新能级,S位缺陷体的禁带区域出现了3条新能级;缺陷体能带结构的能量下降与体系中未成键的电子有关.对于态密度而言,Mo位缺陷体的费米能级处出现了峰值,表明Mo位缺陷会对其光电性质带来影响.同时分析电荷分布发现,Mo缺陷周围存在着负电荷聚集的现象,S缺陷周围存在正电荷聚集的现象.     

Scanning tunneling microscopy with atomic resolution on ReS2 single crystals grown by vapor phase transport

Atomic resolution images of layered transition metal-dichalcogenide ReS₂ single-crystals (n-type semiconductor) were obtained using a scanning tunneling microscope with a positive tip. In most cases only unresolved clusters of four rhenium atoms could be seen. Occasional images with higher resolution showed that these bright structures consist of four separated atoms. The symmetry of the imaged atoms is identical to that of the rhenium sublattice but not to that of the sulfur atoms. We conclude therefore that the main contribution to the tunneling current is due to the rhenium atoms, although the sulfur atoms are placed by about 0.15 nm closer to the tip. Thus for our positive bias of the tip the tunneling electrons originate from occupied rhenium states in the valence band of the semiconductor.     

First-principle investigation of the electronic and magnetic properties of PbMn（SO4）2

The magnetic properties of oxide PbMn(SO₄)₂ consisted of MnO₆ octahedra which connected with each other through SO₄ tetrahedra, are well studied in experiments. In this paper, we explored its interesting electronic and magnetic properties with first-principle calculations. Our results show that all Mn ions have high spin states, namely, S = 5/2, and the magnetic couplings between NN and NNN are antiferromagnetic, which agree well with the experimental results. Besides, the surprising results of spin exchange interactions between the NN and NNN are excellently explained with extended Hückel tight-binding calculations.     

Electronic structures of vacancies in Co_3Sn_2S_2

Co_3Sn_2S_2 has attracted a lot of attention for its multiple novel physical properties, including topological nontrivial surface states, anomalous Hall effect, and anomalous Nernst effect. Vacancies, which play important roles in functional materials, have attracted increasing research attention. In this paper, by using density functional theory calculations, we first obtain band structures and magnetic moments of Co_3Sn_2S_2 with exchange–correlation functionals at different levels. It is found that the generalized gradient approximation gives the positions of Weyl points consistent with experiments in bulk Co_3Sn_2S_2. We then investigate the electronic structures of defects on surfaces with S and Sn terminations which have been observed in experiments. The results show that the single sulfur vacancy on the S-terminated surface introduces localized bond states inside the bandgap near the Fermi level. For di-and tri-sulfur vacancies, the localized defect states hybridize with neighboring ones, forming bonding states as well as anti-bonding states. The Sn vacancy on the Sn-terminated surface also introduces localized bond states, which are merged with the valence bands. These results provide a reference for future experimental investigations of vacancies in Co_3Sn_2S_2.     

Fracture analysis of monolayer graphene sheets with double vacancy defects via MD simulation

Carbon nanostructures such as carbon nanotubes (CNTs) and graphene sheets have attracted great attention due to their exceptionally high strength and elastic strain. These extraordinary mechanical properties, however, can be affected by the presence of defects in their structures. When a material contains multiple defects, it is expected that the stress concentration of them superposes if the separation distances of the defects are low, which causes a more reduction of the strength. On the other hand, it is believed that if the defects are far enough such that their affected areas are distinct, their behavior is similar to a material with single defect. In this article, molecular dynamics (MD) is used to explore the influence of separation distance of double vacancy defects on the mechanical properties of single-layered graphene sheets (SLGSs). To this end, critical stress and strain of SLGSs containing double vacancy with different distances are determined and the results are compared with those of perfect SLGSs and graphene sheets with single vacancy defect. The results reveal that the ultimate strength of the SLGS with double vacancy tends to the one with a single vacancy when the separation distance becomes further. In this regard, the threshold distance beyond which double defects behave like a single one is examined. Finally, Young’s modulus of perfect, single and double vacancy defected graphene sheets with different separation distances is determined. It is concluded that this property is slightly affected by the separation distance.     

Biaxial strain-induced enhancement in the thermoelectric performance of monolayer WSe_2

The effects of biaxial strain on the electronic structure and thermoelectric properties of monolayer WSe_2 have been investigated by using first-principles calculations and the semi-classical Boltzmann transport theory. The electronic band gap decreases under strain, and the band structure near the Fermi level of monolayer WSe_2 is modified by the applied biaxial strain. Furthermore, the doping dependence of the thermoelectric properties of n-and p-doped monolayer WSe_2 under biaxial strain is estimated. The obtained results show that the power factor of n-doped monolayer WSe_2 can be increased by compressive strain while that of p-doping can be increased with tensile strain. Strain engineering thus provides a direct method to control the electronic and thermoelectric properties in these two-dimensional transition metal dichalcogenides materials.     

First-principles studies of electronic,optical,and mechanical properties of γ-Bi_2Sn_2O_7

The detailed theoretical studies of electronic,optical,and mechanical properties of γ-Bi_2Sn_2O_7 are carried out by using first-principle density functional theory calculations.Our calculated results indicate that γ-Bi_2Sn_2O_7 is the p-type semiconductor with an indirect band gap of about 2.72 e V.The flat electronic bands close to the valence band maximum are mainly composed of Bi-6s and O-2p states and play a key role in determining the electrical properties of γ-Bi_2Sn_2O_7.The calculated complex dielectric function and macroscopic optical constants including refractive index,extinction coefficient,absorption coefficients,reflectivity,and electron energy-loss function show that γ-Bi_2Sn_2O_7 is an excellent light absorbing material.The analysis on mechanical properties shows that γ-Bi_2Sn_2O_7 is mechanically stable and highly isotropic.     

Prospects and Opportunities of 2D van der Waals Magnetic Systems

The existence of spontaneous magnetization in low dimensional magnetic systems has attracted intensive studies since the early 60s and research remains very active even now. Only recently, magnetic van der Waals (vdW) systems down to a few layers have been broadly discussed for their magnetic order ground states at finite temperature. The naturally inherited layered structure of the vdW magnetic systems possessing onsite magnetic anisotropy from band electrons can suppress the long-range fluctuations. This provides an excellent vehicle to study the transition of magnetism to 2D limits both theoretically and experimentally. Here the current status of 2D vdW magnetic system and its potential applications are briefly summarized and discussed.     

Strain modulations of magnetism in Fe-doped InSe monolayer

First-principles calculations are performed to investigate the electronic and magnetic characteristics of Fe-doped two-dimensional (2D) InSe monolayer by applying biaxial compressive and tensile strains. Our studies show that Fe substituting indium atom can be realized easily under Se-rich experimental environments, and can induce the magnetic semiconducting characteristics. Interestingly, the magnetic moments are insensitive to the strain ~ −6% to 6% range. However, loading larger tensile strain can decrease the magnetic moments sharply. Moreover, the system still retains semiconducting characteristics under compressive strain, while a transition occurs from semiconductor to metal beyond the tensile strain 8%. These results provide the theoretical predications that Fe-doped 2D InSe material may be applied in the spintronic devices.     

Migration of nitrogen in hexagonal Ge2Sb2Te5: An ab‐initio study

The migration barrier energies of the nitrogen atom and N₂ molecule, and the activation barriers for the dissociation and formation of N₂ in Ge₂Sb₂Te₅ were calculated by ab‐initio methods. Various transition and metastable states were found along the migration pathway. Migration barrier energies up to 1.19 eV for the nitrogen atom suggest that it is difficult for it to move from one site to any other site or diffuse out from Ge₂Sb₂Te₅ although doped nitrogen is energetically less stable with respect to N₂ in vacuum. N₂ in Ge₂Sb₂Te₅ was hardly expected to dissociate into nitrogen atoms and vice versa. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

金红石型TiO_2中四种点缺陷态研究

利用第一性原理计算方法研究了金红石型TiO_2中四种缺陷的电子态.这四种缺陷包括氧空位(O_v)、钛空位(Ti_V)、钛间隙(Ti_S)以及氧空位O_v与钛间隙态Ti_S共存态.氧空位的存在导致禁带内施主缺陷能级较浅,而深施主能级与Ti间隙态有关.预测了氧空位更倾向于与钛间隙结合,主要通过钛间隙态的3d电子部分转移到近邻近氧空位的部分形成O_V-Ti_S对缺陷.具有O_v、Ti_S或O_V-Ti_S缺陷的体系都出现间隙态,促进体系出现红外吸收.