Manipulation of inherent characteristics of graphene through N and Mg atom co-doping; a DFT study

First-principles calculations were performed to investigate the structural, electronic, magnetic and optical properties of nitrogen (N) and magnesium (Mg) atom co-doped graphene systems. We observed that, N and Mg atom co-doping in graphene, introduces half-metallic properties in the electronic structure of graphene, introduces ferromagnetism behavior along with new trends in optical properties of graphene. Doping site and concentration of N and Mg atoms in graphene was changed and resulting effects of these changes on aforementioned properties were investigated. Through density of states plots we observed that, Mg atom sp orbitals mainly induced magnetic moments in graphene. It was revealed that, N/Mg atoms substitution in graphene introduces a red shift in absorption spectrum towards visible range and a finite absorption coefficient quantity value in 0 to 3 eV and 7 to 11 eV energy intervals is also produced, that is unavailable for absorption spectrum of intrinsic graphene. Moreover, N/Mg atoms co-doping produces increment in the reflectivity parameter of graphene in low lying energy region, while producing diminishing behavior in the higher energy range. These results offer a possibility to tune electronic, magnetic and optical characteristics of graphene sufficiently for utilization in graphene based spintronic and optoelectronic devices.     

Adsorption-induced magnetism properties in graphene

Using first-principles calculations, we investigate magnetic properties and electronic structures of graphene with H, N and P adsorptions. With a change in adsorption density from 1/50 to 1/162 a band gap changing from ∼1.2 to 0.1 eV emerges in a H-absorbed graphene, leading to the semiconducting graphene and showing ferromagnetism with the magnetic moment of the system changing from 0.76 to 0.42μ_B. The unpaired electrons in the absorbed N/P atoms are polarized and thus it exhibits magnetic moment per N/P atom changing from 0.38/0.20 to 0.60/0.14μ_B and metallic and half-metallic magnetism, respectively. The spin-polarized graphene system has a great application prospect in spintronics.     

Edge physics of graphene in the quantum Hall regime

We study the electronic edge states of graphene in the quantum Hall regime. For non-interacting electrons, graphene supports both electron-like and hole-like edge states. We find there are half as many edge states of each type in the lowest Landau level compared to higher Landau levels, leading to a quantization of the Hall conductance that is shifted relative to standard two dimensional electron gases. We also consider the effect of quantum Hall ferromagnetism on this edge structure, and find an unusual Luttinger liquid at the edge in undoped graphene. This arises due to a domain wall that forms near the edge between partially spin-polarized and valley-polarized regions. The domain wall has a U(1) degree of freedom which generates both collective and charged gapless excitations, whose consequences for tunneling experiments are discussed.     

Magnetism in disordered graphene and irradiated graphite

The magnetic properties of disordered graphene and irradiated graphite are systematically studied using a combination of mean-field Hubbard model and first-principles calculations. By considering large-scale disordered models of graphene, I conclude that only single-atom defects can induce ferromagnetism in graphene-based materials. The preserved stacking order of graphene layers is shown to be another necessary condition for achieving a finite net magnetic moment of irradiated graphite. Ab initio calculations of hydrogen binding and diffusion and of interstitial-vacancy recombination further confirm the crucial role of stacking order in pi-electron ferromagnetism of proton-bombarded graphite.     

氢化与非氢化石墨烯纳米条带的密度泛函研究

基于密度泛函理论的第一性原理计算方法,研究了宽度N=8的边缘氢化和非氢化条带的结构和电子性质. 研究表明,扶手形无氢化石墨纳米条带的边缘碳原子是以三重键相互结合,它在边缘的成键强度比氢化时要高,具有更强的化学活性,可作为纳米化学传感器的基础材料. 能带结构计算表明,无论是扶手形条带还是锯齿形条带,它们都是具有带隙的半导体,且无氢化条带的带隙要比氢化的条带带隙宽度大,氢化对于条带的电子性质具有显著修饰作用. 通过锯齿形石墨纳米条带顺磁性、铁磁性和反铁磁性的计算,发现反铁磁的状态最稳定,并且边缘磁性最强,这有利于条带在自旋电子器件中的应用. 关键词： 石墨纳米条带 成键机理 电子结构 自旋分布     

Structural,electronic,and magnetic behaviors of 5d transition metal atom substituted divacancy graphene:A first-principles study

Structural, electronic, and magnetic behaviors of 5d transition metal(TM) atom substituted divacancy(DV) graphene are investigated using first-principles calculations. Different 5d TM atoms(Hf, Ta, W, Re, Os, Ir, and Pt) are embedded in graphene, these impurity atoms replace 2 carbon atoms in the graphene sheet. It is revealed that the charge transfer occurs from 5d TM atoms to the graphene layer. Hf, Ta, and W substituted graphene structures exhibit a finite band gap at high symmetric K-point in their spin up and spin down channels with 0.783 μB, 1.65 μB, and 1.78 μB magnetic moments,respectively. Ir and Pt substituted graphene structures display indirect band gap semiconductor behavior. Interestingly, Os substituted graphene shows direct band gap semiconductor behavior having a band gap of approximately 0.4 e V in their spin up channel with 1.5 μB magnetic moment. Through density of states(DOS) analysis, we can predict that d orbitals of 5d TM atoms could be responsible for introducing ferromagnetism in the graphene layer. We believe that our obtained results provide a new route for potential applications of dilute magnetic semiconductors and half-metals in spintronic devices by employing 5d transition metal atom-doped graphene complexes.     

Electronic structure and charge-density wave transition in monolayer VS2

Vanadium disulfide (VS₂) attracts elevated interests for its charge-density wave (CDW) phase transition, ferromagnetism, and catalytic reactivity, but the electronic structure of monolayer has not been well understood yet. Here we report synthesis of epitaxial 1T VS₂ monolayer on bilayer graphene grown by molecular-beam epitaxy (MBE). Angle-resolved photoemission spectroscopy (ARPES) measurements reveal that Fermi surface with six elliptical pockets centered at the M points shows gap opening at low temperature. Temperature-dependence of the gap size suggests existence of CDW phase transition above room temperature. Our observations provide important evidence to understand the strongly correlated electron physics and the related surface catalytic properties in two-dimensional transition-metal dichalcogenides (TMDCs).     

Ferromagnetism in hydrogenated graphene nanopore arrays

Theoretically, the so-called zigzag edge of graphenes provides localized electrons due to the presence of flat energy bands near the Fermi level. Spin interaction makes the localized spins strongly polarized, yielding ferromagnetism. However, in most experimental studies, ferromagnetism has been observed in uncontrollable and complicated carbon-based systems. Here, we fabricate graphenes with honeycomblike arrays of hexagonal nanopores, which have a large ensemble of hydrogen-terminated and low-defect pore edges that are prepared by a nonlithographic method (nanoporous alumina templates). We observe large-magnitude ferromagnetism derived from electron spins localizing at the zigzag nanopore edges. This promises to be a realization of graphene magnets and novel spintronic devices.     

Magnetic and electronic properties of two-dimensional metal-organic frameworks TM_3(C_2NH)_(12)

The ferromagnetism of two-dimensional(2 D) materials has aroused great interest in recent years, which may play an important role in the next-generation magnetic devices. Herein, a series of 2 D transition metal-organic framework materials(TM-NH MOF, TM = Sc–Zn) are designed, and their electronic and magnetic characters are systematically studied by means of first-principles calculations. Their structural stabilities are examined through binding energies and abinitio molecular dynamics simulations. Their optimized lattice constants are correlated to the central TM atoms. These 2 D TM-NH MOF nanosheets exhibit various electronic and magnetic performances owing to the effective charge transfer and interaction between TM atoms and graphene linkers. Interestingly, Ni-and Zn-NH MOFs are nonmagnetic semiconductors(SM) with band gaps of 0.41 e V and 0.61 e V, respectively. Co-and Cu-NH MOFs are bipolar magnetic semiconductors(BMS), while Fe-NH MOF monolayer is a half-semiconductor(HSM). Furthermore, the elastic strain could tune their magnetic behaviors and transformation, which ascribes to the charge redistribution of TM-3 d states. This work predicts several new 2 D magnetic MOF materials, which are promising for applications in spintronics and nanoelectronics.     

Effects of topological defects and local curvature on the electronic properties of planar graphene

A formalism is proposed to study the electronic and transport properties of graphene sheets with corrugations as the one recently synthesized. The formalism is based on coupling the Dirac equation that models the low energy electronic excitations of clean flat graphene samples to a curved space. A cosmic string analogy allows to treat an arbitrary number of topological defects located at arbitrary positions on the graphene plane. The usual defects that will always be present in any graphene sample as pentagon–heptagon pairs and Stone–Wales defects are studied as an example. The local density of states around the defects acquires characteristic modulations that could be observed in scanning tunnel and transmission electron microscopy.     

Weyl-gauge symmetry of graphene

The conformal invariance of the low energy limit theory governing the electronic properties of graphene is explored. In particular, it is noted that the massless Dirac theory in point enjoys local Weyl symmetry, a very large symmetry. Exploiting this symmetry in the two spatial dimensions and in the associated three dimensional spacetime, we find the geometric constraints that correspond to specific shapes of the graphene sheet for which the electronic density of states is the same as that for planar graphene, provided the measurements are made in accordance to the inner reference frame of the electronic system. These results rely on the (surprising) general relativistic-like behavior of the graphene system arising from the combination of its well known special relativistic-like behavior with the less explored Weyl symmetry. Mathematical structures, such as the Virasoro algebra and the Liouville equation, naturally arise in this three-dimensional context and can be related to specific profiles of the graphene sheet. Speculations on possible applications of three-dimensional gravity are also proposed.     

Spontaneous parity breaking of graphene in the Quantum Hall regime

We propose that the inversion symmetry of the graphene honeycomb lattice is spontaneously broken via a magnetic-field-dependent Peierls distortion. This leads to valley splitting of the n=0 Landau level but not of the other Landau levels. Compared to Quantum Hall valley ferromagnetism recently discussed in the literature, lattice distortion provides an alternative explanation to all of the currently observed Quantum Hall plateaus in graphene.     

A cosmological model for corrugated graphene sheets

Defects play a key role in the electronic structure of graphene layers flat or curved. Topological defects in which an hexagon is replaced by an n-sided polygon generate long range interactions that make them different from vacancies or other potential defects. In this work we review previous models for topological defects in graphene. A formalism is proposed to study the electronic and transport properties of graphene sheets with corrugations as the one recently synthesized. The formalism is based on coupling the Dirac equation that models the low energy electronic excitations of clean flat graphene samples to a curved space. A cosmic string analogy allows to treat an arbitrary number of topological defects located at arbitrary positions on the graphene plane. The usual defects that will always be present in any graphene sample as pentagon–heptagon pairs and Stone-Wales defects are studied as an example. The local density of states around the defects acquires characteristic modulations that could be observed in scanning tunnel and transmission electron microscopy.     

Point defects on graphene on metals

Understanding the coupling of graphene with its local environment is critical to be able to integrate it in tomorrow's electronic devices. Here we show how the presence of a metallic substrate affects the properties of an atomically tailored graphene layer. We have deliberately introduced single carbon vacancies on a graphene monolayer grown on a Pt(111) surface and investigated its impact in the electronic, structural, and magnetic properties of the graphene layer. Our low temperature scanning tunneling microscopy studies, complemented by density functional theory, show the existence of a broad electronic resonance above the Fermi energy associated with the vacancies. Vacancy sites become reactive leading to an increase of the coupling between the graphene layer and the metal substrate at these points; this gives rise to a rapid decay of the localized state and the quenching of the magnetic moment associated with carbon vacancies in freestanding graphene layers.     

Ferromagnetism driven by intrinsic point defects in HfO(2)

In view of recent experimental reports of unexpected ferromagnetism in HfO(2) thin films, we carried out first-principles investigations looking for magnetic order possibly brought about by the presence of small concentrations of intrinsic point defects. Ab initio electronic structure calculations using density functional theory show that isolated cation vacancy sites in HfO(2) lead to the formation of high-spin defect states. Furthermore these appear to be ferromagnetically coupled with a rather short range magnetic interaction, resulting in a ferromagnetic ground state for the whole system. More interestingly, the occurrence of these high-spin states and ferromagnetism is in the low symmetry monoclinic phase of HfO(2). This is radically different from other systems previously known to exhibit point defect ferromagnetism, warranting a closer look at the phenomenon.     

Effect of impurity ions configurations on the magnetic properties of Mn-doped ZnO

The magnetic and electronic properties of Mn-doped ZnO are studied by first-principles calculations. It is found that the exchange interaction between Mn ions depends on the Mn-Mn distribution configuration and distance. We also found that the ferromagnetism can be existed when the Mn-Mn distance is large and Mn ions are distributed uniformly, and the long ranged ferromagnetism is explained by the interaction between Mn and O atoms. Thus, it is possible to tune ferromagnetism in Mn-doped ZnO semiconductors by controlling the doping position in ZnO lattice.     

Limits on intrinsic magnetism in graphene

We have studied magnetization of graphene nanocrystals obtained by sonic exfoliation of graphite. No ferromagnetism is detected at any temperature down to 2?K. Neither do we find strong paramagnetism expected due to the massive amount of edge defects. Rather, graphene is strongly diamagnetic, similar to graphite. Our nanocrystals exhibit only a weak paramagnetic contribution noticeable below 50?K. The measurements yield a single species of defects responsible for the paramagnetism, with approximately one magnetic moment per typical graphene crystallite.     

Quantum spin Hall effect in graphene

We study the effects of spin orbit interactions on the low energy electronic structure of a single plane of graphene. We find that in an experimentally accessible low temperature regime the symmetry allowed spin orbit potential converts graphene from an ideal two-dimensional semimetallic state to a quantum spin Hall insulator. This novel electronic state of matter is gapped in the bulk and supports the transport of spin and charge in gapless edge states that propagate at the sample boundaries. The edge states are nonchiral, but they are insensitive to disorder because their directionality is correlated with spin. The spin and charge conductances in these edge states are calculated and the effects of temperature, chemical potential, Rashba coupling, disorder, and symmetry breaking fields are discussed.     

Electronic properties and tunability in graphene/3D-InP mixed-dimensional van der Waals heterostructure

InP solar cell is promising for space application due to its strong space radiation resistance and high power conversion efficient (PCE). Graphene/InP heterostructure solar cell is expected to have a higher PCE because strong near-infrared light can also be absorbed and converted additionally by graphene in this heterostructure. However, a low PCE was reported experimentally for Graphene/InP heterostructures. In this paper, electronic properties of graphene/InP heterostructures are calculated using density functional theory to understand the origin of the low PCE and propose possible improving ways. Our calculation results reveal that graphene contact with InP form a p-type Schottky heterostructure with a low Schottky barrier height (SBH). It is the low SBH that leads to the low PCE of graphene/InP heterostructure solar cells. A new heterostructure, graphene/insulating layer/InP solar cells, is proposed to raise SBH and PCE. Moreover, we also find that the opened bandgap of graphene and SBH in graphene/InP heterostructures can be tuned by exerting an electric field, which is useful for photodetector of graphene/InP heterostructures.     

Magnetotransport properties of graphene layers decorated with colloid quantum dots

The hybrid graphene-quantum dot devices can potentially be used to tailor the electronic, optical, and chemical properties of graphene. Here, the low temperature electronic transport properties of bilayer graphene decorated with PbS colloid quantum dots(CQDs) have been investigated in the weak or strong magnetic fields. The presence of the CQDs introduces additional scattering potentials that alter the magnetotransport properties of the graphene layers, leading to the observation of a new set of magnetoconductance oscillations near zero magnetic field as well as the high-field quantum Hall regime.The results bring about a new strategy for exploring the quantum interference effects in two-dimensional materials which are sensitive to the surrounding electrostatic environment, and open up a new gateway for exploring the graphene sensing with quantum interference effects.