We describe the effects of vacancies on the electronic properties of a graphene sheet in the presence of a perpendicular magnetic field: from a single defect to an organized vacancy lattice. An isolated vacancy is the minimal possible inner edge, showing an antidotlike behaviour, which results in an extra level between consecutive Landau levels. Two close vacancies may couple to each other, forming a vacancy molecule tuned by the magnetic field. We show that a vacancy lattice introduce an extra band in between Landau levels with localization properties that could lead to extra Hall resistance plateaus.
We report anomalous quantum transport features in bilayer graphene in presence of a random distribution of structural vacancies. By using an efficient real-space Kubo-Greenwood transport methodology, the impact of a varying density of dimer versus non-dimer vacancies is investigated in very large scale disordered models. While non-dimer vacancies are shown to induce localization regimes, dimer vacancies result in an unexpected ballistic regime whose energy window surprisingly enlarges with increasing impurity density. Such counterintuitive phenomenon is explained by the formation of an effecti…
The graphene and phosphorene nanostructures have a big potential application in a large area of actuals research in physics. However, their methods of synthesis still do not allow the production of perfect materials with an intact molecular structure. In this paper, the occurrence of atomic vacancies was considered in the edge structure of the zigzag phosphorene and graphene nanoribbons. For different concentrations of these edge vacancies, their influence on the metallic properties was investigated. The calculations were performed for different sizes of the unit cell. Furthermore, for a small…
Graphene clusters consisting of 24 to 150 carbon atoms and hydrogen termination at the zigzag boundary edges have been studied, as well as clusters disordered by vacancy(s). Density Function Theory and Gaussian03 software were used to calculate graphene relative stability, desorption energy, band gap, density of states, surface shape, dipole momentum and electrical polarization of all clusters by applying the hybrid exchange-correlation functional Beke-Lee-Yang-Parr. Furthermore, infrared frequencies were calculated for two of them. Different basis sets, 6-31g**, 6-31g* and 6-31g, depending on…
The effect of electronic interactions in graphene with vacancies or resonant scatterers is investigated. We apply dynamical mean-field theory in combination with quantum Monte Carlo simulations, which allow us to treat non-perturbatively quantum fluctuations beyond Hartree-Fock approximations. The interactions narrow the width of the resonance and induce a Curie magnetic susceptibility, signaling the formation of local moments. The absence of saturation of the susceptibility at low temperatures suggests that the coupling between the local moment and the conduction electrons is ferromagnetic.
In order to investigate the interaction between single vacancies in a graphene sheet, we have used spin-polarized density functional theory (DFT). Two distinct configurations were considered, either with the two vacancies located in the same sublattice or in different sublattices, and the effect of changing the separation between the vacancies was also studied. Our results show that the ground state of the system is indeed magnetic, but the presence of the vacancies in the same sublattice or in different sublattices and the possible topological configurations can lead to different contribution…
Graphene nanoflakes are interesting because electrons are naturally confined in these quasi-zero-dimensional structures, whereas confinement in bulk graphene would require a band gap. Vacancies inside the graphene lattice lead to localized states and the spins of such localized states may be used for spintronics. We perform a tight-binding description of a nanoflake with two vacancies and include a perpendicular magnetic field via a Peierls phase. The tunnel coupling strength and from it the exchange coupling between the localized states can be obtained from the energy splitting between numeri…
The interaction of two resonant impurities in graphene has been predicted to have a long-range character with weaker repulsion when the two adatoms reside on the same sublattice and stronger attraction when they are on different sublattices. We reveal that this attraction results from a single energy level. This opens up a possibility of controlling the sign of the impurity interaction via the adjustment of the chemical potential. For many randomly distributed impurities (adatoms or vacancies) this may offer a way to achieve a controlled transition from aggregation to dispersion.
We report {\it ab initio} calculations of the structural, electronic and magnetic properties of a graphene monolayer substitutionally doped with Co (Co$_{sub}$) atoms. We focus in Co because among traditional ferromagnetic elements (Fe, Co and Ni), only Co$_{sub}$ atoms induce spin-polarization in graphene. Our results show the complex magnetism of Co substitutional impurites in graphene, which is mapped into simple models such as the $π$-vacancy and Heisenberg model. The links established in our work can be used to bring into contact the engineering of nanostructures with the results of $π$-m…
Vacancy-induced magnetization of a graphene layer is investigated by means of a first principle DFT method. Calculations of the formation energy and the magnetization by creating the different number of vacancies in a supercell show that a clustering with big number of vacancies in the cluster is rather favorable than that of isolated vacancies, homogeneously distributed in the layer. The magnetic moment of a cluster with big number of vacancies is shown to be not proportional with the vacancy concentration, which is in good agreement with the recent experimental results. Our studies support t…
We investigate electronic transport in the nitrogen-doped graphene containing different configurations of point defects: singly or doubly substituting N atoms and nitrogen-vacancy complexes. The results are numerically obtained using the quantum-mechanical Kubo-Greenwood formalism. Nitrogen substitutions in graphene lattice are modelled by the scattering potential adopted from the independent self-consistent ab initio calculations. Variety of quantitative and qualitative changes in the conductivity behaviour are revealed for both graphite- and pyridine-type N defects in graphene. For the most …
Electronic and magnetic properties of a system of two charged vacancies in hexagonal shaped graphene quantum dots are investigated using a mean-field Hubbard model as a function of the Coulomb potential strength $β$ of the charge impurities and the distance R between them. For $β=0$, the magnetic properties of the vacancies are dictated by Lieb's rules where the opposite (same) sub-lattice vacancies are coupled antiferromagnetically (ferromagnetically) and exhibit Fermi oscillations. Here, we demonstrate the emergence of a non-magnetic regime within the subcritical region: as the Coulomb poten…
We study the effects of a low concentration of adatoms or single vacancies in the linear-response transport properties of otherwise clean graphene. These impurities were treated as localized orbitals, and for each type two cases with distinct coupling symmetries were studied. For adatoms, we considered top- and hollow-site adsorbates (TOP and HS). For vacancies, we studied impurity formation by soft bond reconstruction (REC), as well as the more symmetric case of charge accumulation in unreconstructed vacancies (VAC). Our results indicate that the transport is determined by usual impurity scat…
Using first-principles plane wave calculations we predict that electronic and magnetic properties of graphene nanoribbons can be affected by defect-induced itinerant states. The band gaps of armchair nanoribbons can be modified by hydrogen saturated holes. Defects due to periodically repeating vacancy or divacancies induce metallization, as well as magnetization in non-magnetic semiconducting nanoribbons due to the spin-polarization of local defect states. Antiferromagnetic ground state of semiconducting zigzag ribbons can change to ferrimagnetic state upon creation of vacancy defects, which r…
The effect of vacancies on the robustness of zero-energy edge electronic states in zigzag-type graphene layer is studied at different concentrations and distributions of defects. All calculations are performed by using the Green's function method and the tight-binding approximation. It is found that the arrangement of defects plays a crucial role in the destruction of the edge states. We have specified a critical distance between edge vacancies when their mutual influence becomes significant and affects markedly the density of electronic states at graphene edge.
The coherent electron transport along zigzag and metallic armchair graphene nanoribbons in the presence of one or two vacancies is investigated. Having in mind atomic scale tunability of the conductance fingerprints, the primary focus is on the effect of the distance to the edges and inter vacancies spacing. An involved interplay of vacancies sublattice location and nanoribbon edge termination, together with the spacing parameters lead to a wide conductance resonance line shape modification. Turning on a magnetic field introduces a new length scale that unveils counter-intuitive aspects of the…
We present an ab initio study on the structural and electronic distortions of modified graphene by creation of vacancies, inclusion of boron atoms, and the coexistence of both, by means of thermodynamics and band structure calculations. In the case of coexistence of boron atoms and vacancy, the modified graphene presents spin polarization only when B atoms locate far from vacancy. Thus, when a boron atom fills single- and di-vacancies, it suppresses the spin polarization of the charge density. In particular when B atoms fill a di-vacancy a new type of rearrangement occurs, where a stable BC4 u…
Among two-dimensional atomic crystals, hexagonal boron nitride (hBN) is one of the most remarkable materials to fabricate heterostructures revealing unusual properties. We perform first-principles calculations to determine whether intercalated metal atoms and vacancies can mediate interfacial coupling and influence the structural and electronic properties of the graphene/hBN heterostructure. Metal impurity atoms (Li, K, Cr, Mn, Co, and Cu) as extrinsic defects between the graphene and hBN sheets produce $n$-doped graphene. We also consider intrinsic vacancy defects and find that a boron monova…
The influence of edge vacancies on the working ability of the planar graphene tunnel field-effect transistor (TFET) is studied at various concentrations and distributions (normal, uniform, periodic) of defects. All calculations are performed by using the Green's function method and the tight-binding approximation. It is shown that the transistor performance depends critically on two important factors associated with the defects: the destruction of the edge-localized electronic states and the emergence of subpeaks near the Fermi level. The supportable operation conditions of the TFET are found …
The influence of periodic edge vacancies and antidot arrays on the thermoelectric properties of zigzag graphene nanoribbons is investigated. Using the Green's function method, the tight-binding approximation for the electron Hamiltonian and the 4th nearest neighbor approximation for the phonon dynamical matrix, we calculate the Seebeck coefficient and the thermoelectric figure of merit. It is found that, at a certain periodic arrangement of vacancies on both edges of zigzag nanoribbon, a finite band gap opens and almost twofold degenerate energy levels appear. As a result, a marked increase in…
The study of vacancies in graphene is a topic of growing interest. A single vacancy induces a localized stable charge of order unity interacting with other charges of the conductor through an unscreened Coulomb potential. It also breaks the symmetry between the two triangular graphene sublattices hence inducing zero energy states at the Dirac points. Here we show the fractional and pseudo-scalar nature of this vacancy charge. A continuous Dirac model is presented which relates zero modes to vacuum fractional charge and to a parity anomaly. This relation constitutes an Index theorem and is achi…
Using the tight-binding model, we investigate the influence of vacancy disorder on electrical transport in graphene Hall bars in the presence of quantizing magnetic fields. Disorder, induced by a random distribution of monovacancies, breaks the graphene sublattice symmetry and creates states localized on the vacancies. These states are observable in the bend resistance, as well as in the total DOS. Their energy is proportional to the square root of the magnetic field, while their localization length is proportional to the cyclotron radius. At the energies of these localized states, the electro…
Vacancies in graphene lead to the appearance of localized electronic states with non-vanishing spin moments. Using a mean-field Hubbard model and an effective double-quantum dot description we investigate the influence of strain on localization and magnetic properties of the vacancy-induced states in semiconducting armchair nanoribbons. We find that the exchange splitting of a single vacancy and the singlet-triplet splitting for two vacancies can be widely tuned by applying uniaxial strain, which is crucial for spintronic applications.
In this work the Casimir{Polder interaction energy between a rubidium atom and a disordered graphene sheet is investigated beyond the Dirac cone approximation by means of accurate real-space calculations. As a model of defected graphene, we consider a tight-binding model of Π-electrons on a honeycomb lattice with a small concentration of point defects. The optical response of the graphene sheet is evaluated with full spectral resolution by means of exact Chebyshev polynomial expansions of the Kubo formula in large lattices with in excess of ten million atoms. At low temperatures, the optical r…
We study the properties of localized vibrational modes associated with structural defects in a sheet of graphene. For the example of the Stone-Wales defects, one- and two-atom vacancies, many-atom linear vacancies, and adatoms in a honeycomb lattice, we demonstrate that the local defect modes are characterized by stable oscillations with the frequencies lying outside the linear frequency bands of an ideal graphene. In the frequency spectral density of thermal oscillations, such localized defect modes lead to the additional peaks from the right side of the frequency band of the ideal sheet of g…
Chemical vapor deposition (CVD) on Cu foil is one of the most promising methods to produce graphene samples despite of introducing numerous grain boundaries into the perfect graphene lattice. A rich variety of GB structures can be realized experimentally by controlling the parameters in the CVD method. Grain boundaries contain non-hexagonal carbon rings (4,5,7,8 membered rings) and vacancies in various ratios and arrangements. Using wave packet dynamic (WPD) simulations and tight-binding electronic structure calculations, we have studied the effect of the structure of GBs on the transport prop…
We present a systematic study of electron backscattering phenomena during conduction for graphene nanoribbons with single-vacancy scatterers and dimensions within the capabilities of modern lithographic techniques. Our analysis builds upon an \textit{ab initio} parameterized semiempirical model that breaks electron-hole symmetry and nonequilibrium Green's function methods for the calculation of the conductance distribution $g$. The underlying mechanism is based on wavefunction localizations and perturbations that in the case of the first $π-π^*$ plateau can give rise to impurity-like pseudogap…
The observation of intrinsic magnetic order in graphene and graphene-based materials relies on the formation of magnetic moments and a sufficiently strong mutual interaction. Vacancies are arguably considered the primary source of magnetic moments. Here we present an in-depth density functional theory study of the spin-resolved electronic structure of (monoatomic) vacancies in graphene and bilayer graphene. We use two different methodologies: supercell calculations with the SIESTA code and cluster-embedded calculations with the ALACANT package. Our results are conclusive: The vacancy-induced e…
We investigate the effects of vacancies, disorder and sublattice polarization on the electronic properties of a monolayer graphene in the quantum Hall regime. Energy spectra as a function of magnetic field and the localization properties of the states within the graphene Landau levels (LLs) are calculated through a tight-binding model. We first discuss our results considering vacancies in the lattice, where we show that vacancies introduce extra levels (or well-defined bands) between consecutive LLs. An striking consequence here is that extra Hall resistance plateaus are expected to emerge whe…
Monolayer graphene grown by chemical vapor deposition and transferred to SiO_2 is used to introduce vacancies by Ar^+ ion bombardment at a kinetic energy of 50 eV. The density of defects visible in scanning tunneling microscopy (STM) is considerably lower than the ion fluence implying that most of the defects are single vacancies. The vacancies are characterized by scanning tunneling spectroscopy (STS) on graphene and HOPG exhibiting a peak close to the Fermi level. The peak persists after air exposure up to 180 min, albeit getting broader. After air exposure for less than 60 min, electron spi…
The electronic structure, bonding and magnetism in graphene containing vacancies are studied using density-functional methods. The single-vacancy graphene ground state is spin polarized and structurally flat. The unpolarized state is non planar only for finite segments. Systems containing periodic arrays of vacancies displays magnetic transitions and metal-insulator transitions.
The density of states (DoS), $\varrho(E)$, of graphene is investigated numerically and within the self-consistent T-matrix approximation (SCTMA) in the presence of vacancies within the tight binding model. The focus is on compensated disorder, where the concentration of vacancies, $n_\text{A}$ and $n_\text{B}$, in both sub-lattices is the same. Formally, this model belongs to the chiral symmetry class BDI. The prediction of the non-linear sigma-model for this class is a Gade-type singularity $\varrho(E) \sim |E|^{-1}\exp(-|\log(E)|^{-1/x})$. Our numerical data is compatible with this result in…
In this communication we present together four distinct techniques for the study of electronic structure of solids : the tight-binding linear muffin-tin orbitals (TB-LMTO), the real space and augmented space recursions and the modified exchange-correlation. Using this we investigate the effect of random vacancies on the electronic properties of the carbon hexagonal allotrope, graphene, and the non-hexagonal allotrope, planar T graphene. We have inserted random vacancies at different concentrations, to simulate disorder in pristine graphene and planar T graphene sheets. The resulting disorder, …
In this proceedings paper we report on a calculation of graphene's Landau levels in a magnetic field. Our calculations are based on a self-consistent Hartree-Fock approximation for graphene's massless-Dirac continuum model. We find that because of graphene's chiral band structure interactions not only shift Landau-level energies, as in a non-relativistic electron gas, but also alter Landau level wavefunctions. We comment on the subtle continuum model regularization procedure necessary to correctly maintain the lattice-model's particle hole symmetry properties.
Massless Dirac electrons in graphene fill Landau levels with energies scaled as square roots of their numbers. Coulomb interaction between electrons leads to mixing of different Landau levels. The relative strength of this interaction depends only on dielectric susceptibility of surrounding medium and can be large in suspended graphene. We consider influence of Landau level mixing on the properties of magnetoexcitons and magnetoplasmons - elementary electron-hole excitations in graphene in quantizing magnetic field. We show that, at small enough background dielectric screening, the mixing lead…
Layer stacking and crystal lattice symmetry play important roles in the band structure and the Landau levels of multilayer graphene. ABA-stacked trilayer graphene possesses mirror-symmetry-protected monolayer-like and bilayer-like band structures. Broken mirror symmetry by a perpendicular electric field therefore induces hybridization between these bands and various quantum Hall phases emerge. We experimentally explore the evolution of Landau levels in ABA-stacked trilayer graphene under electric field. We observe a variety of valley and orbital dependent Landau level evolutions. These evoluti…
We employ the Green's function technique to investigate the vacancy-induced quasi-localized magnetic moment formation in mono-layer graphene starting with the Dirac Hamiltonian, which focuses on the π- orbitals only, involving the nearest neighbor(NN)(t) and moderate second neighbor(SN)(t' < t/3) hopping integrals. The vacancy defect is modeled by the addition of the on-site perturbation potential to the Hamiltonian. We find that, when (t'/t) << 1, the vacancy induced π-state at the zero of energy(zero-mode state(ZMS)) does not inhabit the minority sub-lattice due to the strong scalar potentia…
The presence of defects such as vacancies in solids has prominent effects on their mechanical properties. It not only modifies the stiffness and strength of materials, but also changes their morphologies. The latter effect is extremely significant for low- dimensional materials such as graphene. We show in this work that graphene swells while point defects such as vacancies are created at finite concentrations. The distorted geometry resulted from this areal expansion, in combination with the in-plane softening effect, predicts an unusual defect concentration dependence of stiffness measured f…
Graphene, with its massless linearly-dispersing carriers, in the quantum Hall regime provides an instructive comparison with conventional two-dimensional (2D) systems in which carriers have a nonzero band mass and quadratic dispersion. We investigate the influence of Landau level mixing in graphene on Wigner crystal states in the $n^\mathrm{th}$ Landau level obtained using single Landau level approximation. We show that the Landau level mixing does not qualitatively change the phase diagram as a function of partial filling factor $ν$ in the $n^\mathrm{th}$ level. We find that the inter-Landau …
In a magnetic field graphene trilayers support a characteristic multiplet of 12 zero(-energy)-mode Landau levels with a threefold degeneracy in Landau orbitals. It was earlier noted for bilayer graphene that Coulombic vacuum fluctuations, specific to graphene, lift the orbital degeneracy of such zero-energy modes and that these Lamb-shfted" orbital modes, with filling, get mixed via the Coulomb interaction. It is pointed out that analogous orbital Lamb shift and mixing of zero-mode levels can also take place, with an enriched symmetry content, in ABC-stacked trilayer graphene; and its conseque…
Density of states (DOS) of graphene under a high uniform magnetic field and white-noise random potential is numerically calculated. The disorder broadened zero-energy Landau band has a Gaussian shape whose width is proportional to the random potential variance and the square root of magnetic field. Wegner-type calculation is used to justify the results.
The electronic spectrum of three coupled graphene layers (graphene trilayers) is investigated in the presence of an external magnetic field. We obtain analytical expressions for the Landau level spectrum for both the ABA and ABC - type of stacking, which exhibit very different dependence on the magnetic field. The effect of layer asymmetry and of external gate voltages can strongly influence the properties of the system.
We study the relaxation dynamics of the electron system in graphene flakes under Landau quantization regime using a novel approach of time-resolved Raman scattering. The non-resonant character of the experiment allows us to analyze the field dependence of the relaxation rate. Our results clearly evidence sharp increase in the relaxation rate upon the resonance between the energy of the Landau transition and the G-band and shed new light on relaxation mechanism of the Landau-quantized electrons in graphene beyond the previously studied Auger scattering.
We investigate the superfluid properties of disordered double layer graphene systems using the non-equilibrium Green's function (NEGF) formalism. The complexity of such a structure makes it imperative to study the effects of lattice vacancies which will inevitably arise during fabrication. We present and compare room temperature performance characteristics for both ideal and disordered bilayer graphene systems in an effort to illustrate the behavior of a Bose-Einstein Condensate in the presence of lattice defects under non-equilibrium conditions. We find that lattice vacancies spread throughou…
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 broa…
Magnetotransport measurements are performed in ultraclean (lithographically patterned) graphene nanoribbons down to 70 nm. At high magnetic fields, a fragmentation of the electronic spectrum into a Landau levels pattern with unusual features is unveiled. The singular Landau spectrum reveals large magneto-oscillations of the Fermi energy and valley degeneracy lifting. Quantum simulations suggest some disorder threshold at the origin of mixing between opposite chiral magnetic edge states and disappearance of quantum Hall effect.
Interaction driven integer quantum Hall effects are anticipated in graphene bilayers because of the near-degeneracy of the eight Landau levels which appear near the neutral system Fermi level. We predict that an intra-Landau-level cyclotron resonance signal will appear at some odd-integer filling factors, accompanied by collective modes which are nearly gapless and have approximate $k^{3/2}$ dispersion. We speculate on the possibility of unususal localization physics associated with these modes.
We study the discrete energy spectrum of curved graphene sheets in the presence of a magnetic field. The shifting of the Landau levels is determined for complex and realistic geometries of curved graphene sheets. The energy levels follow a similar square root dependence on the energy quantum number as for rippled and flat graphene sheets. The Landau levels are shifted towards lower energies proportionally to the average deformation and the effect is larger compared to a simple uni-axially rippled geometry. Furthermore, the resistivity of wrinkled graphene sheets is calculated for different ave…
The density of states, $\varrho(E)$, of graphene is investigated within the tight binding (Hückel) approximation in the presence of vacancies. They induce a non-vanishing density of zero modes, $n_\text{zm}$, that act as midgap states: $\varrho(E)=n_\text{zm}δ(E) + \text{smooth}$. As is well known, the actual number of zero modes per sample can in principle exceed the sublattice imbalance: $N_\text{zm}\geq |N_\text{A}-N_\text{B}|$, where $N_\text{A}$, $N_\text{B}$ denote the number of carbon atoms in each sublattice. In this work, we establish a stronger relation that is valid in the thermodyn…
A single graphene layer exhibits an anomalous Landau level spectrum. A massless Dirac like low energy electronic spectrum underlies this anomaly. We study, analytically and numerically, the effect of a uniform electric field $(E)$ on the anomalous Landau levels. We solve the problem exactly within the Dirac cone approximation and find an interesting scaling of the spectrum, leading to the collapse of the Landau levels at a critical $E_c(B)$, for a given magnetic field $B$. We offer a physical interpretation of our result, which uses `graphene relativity' and the boost operation. Electric field…
Atomic vacancies have a strong impact in the mechanical, electronic and magnetic properties of graphene-like materials. By artificially generating isolated vacancies on a graphite surface and measuring their local density of states on the atomic scale, we have shown how single vacancies modify the electronic properties of this graphene-like system. Our scanning tunneling microscopy experiments, complemented by tight binding calculations, reveal the presence of a sharp electronic resonance at the Fermi energy around each single graphite vacancy, which can be associated with the formation of loc…
We study nonlinear optical response of Landau quantized graphene to an intense electromagnetic wave. In particular, we consider high harmonic generation process. It is shown that one can achieve efficient generation of high harmonics with strong radiation fields -- when the work of the wave electric field on the magnetic length is larger than pump photon energy. At that high harmonics generation process takes place for a wide range of the pump wave frequencies and intensities even for significant broadening of Landau levels because of impurities in graphene.
