We calculate the diffusion barrier of fluorine adatoms on doped graphene in the diluted limit using Density Functional Theory. We found that the barrier $Δ$ strongly depends on the magnitude and character of the graphene's doping ($δn$): it increases for hole doping ($δn<0$) and decreases for electron doping ($δn>0$). Near the neutrality point the functional dependence can be approximately by $Δ=Δ_0-α\, δn$ where $α\simeq6\times10^{-12}$ meVcm$^2$. This effect leads to significant changes of the diffusion constant with doping even at room temperature and could also affect the low temperature diffusion dynamics due to the presence of substrate induced charge puddles. In addition, this might open up the possibility to engineer the F dynamics on graphene by using local gates.
We report on theoretical investigations of the spin-orbit coupling effects in fluorinated graphene. First-principles density functional calculations are performed for the dense and dilute adatom coverage limits. The dense limit is represented by the single-side semifluorinated graphene, which is a metal with spin-orbit splittings of about 10 meV. To simulate the effects of a single adatom, we also calculate the electronic structure of a $10 \times 10$ supercell, with one fluorine atom in the top position. Since this dilute limit is useful to study spin transport and spin relaxation, we also in…
Adatom-decorated graphene offers a promising new path towards spintronics in the ultrathin limit. We combine experiment and theory to investigate the electronic properties of dilutely fluorinated bilayer graphene, where the fluorine adatoms covalently bond to the top graphene layer. We show that fluorine adatoms give rise to resonant impurity states near the charge neutrality point of the bilayer, leading to strong scattering of charge carriers and hopping conduction inside a field-induced band gap. Remarkably, the application of an electric field across the layers is shown to tune the resonan…
Recent experimental evidence that fluorinated graphene creates local magnetic moments around F adatoms has not been supported by semilocal density-functional theory (DFT) calculations where the adsorption of an isolated F adatom induces no magnetic moment in graphene. Here, we show that such an incorrect prediction of the nonmagnetic ground state is due to the self-interaction error inherent in semilocal exchange-correlation functionals. The present hybrid DFT calculation for an isolated F adatom on graphene predicts not only a spin-polarized ground state with a spin moment of 1 bohr magneton,…
We present a joint experiment-theory study on the role of fluorine adatoms in spin and momentum scattering of charge carriers in dilute fluorinated graphene and bilayer graphene. The experimental spin-flip and momentum scattering rates and their dependence on the density of fluorine and carrier doping are obtained through weak localization and conductivity measurements, respectively, and suggest the role of fluorine as resonant magnetic impurities. For the estimated fluorine concentration of a few 100 ppm, the observed spin lifetimes are in the range of 1-10\,ps. Theoretically, we established …
We study the dynamics of optically-induced nuclear spin polarization in a fluorine-doped ZnSe epilayer via time-resolved Kerr rotation. The nuclear polarization in the vicinity of a fluorine donor is induced by interaction with coherently precessing electron spins in a magnetic field applied in the Voigt geometry. It is detected by nuclei-induced changes in the electron spin coherence signal. This all-optical technique allows us to measure the longitudinal spin relaxation time $T_{1}$ of the $^{77}\text{Se}$ isotope in a magnetic field range from 10 to 130~mT under illumination. We combine the…
We analyze the origin of spin-orbit coupling (SOC) in fluorinated graphene using Density Functional Theory (DFT) and a tight-binding model for the relevant orbitals. As it turns out, the dominant source of SOC is the atomic spin-orbit of fluorine adatoms and not the impurity induced SOC based on the distortion of the graphene plane as in hydrogenated graphene. More interestingly, our DFT calculations show that SOC is strongly affected by both the type and concentrations of the graphene's carriers, being enhanced by electron doping and reduced by hole doping. This effect is due to the charge tr…
We analyze the electronic properties of adatom doped graphene in the low impurity concentration regime. We focus on the Anderson localized regime and calculate the localization length ($ξ$) as a function of the electron doping and an external magnetic field. The impurity states hybridize with carbon's $p_z$ states and form a partially filled band close to the Dirac point. Near the impurity band center, the chiral symmetry of the system's effective Hamiltonian is partially preserved which leads to a large enhancement of $ξ$. The sensitivity of transport properties, namely Mott's variable range …
Density functional modeling of atomic structure and calculation of electronic structure of one-side one-sublattice functionalized graphene (graphone) are performed for hydrogen and fluorine adatoms. Shown that using of fluorine for functionalization not on enhance stability of compound but also provide switch of magnetic ground state from ferro- to antiferromagnetic. Half-metallic ferromagnetic state in fluorine based graphone is also discussed.
Early experiments on alkali-doped graphene demonstrated that the dopant adatoms modify the conductivity of graphene significantly, as extra carriers enhance conductivity while Coulomb scattering off the adatoms suppresses it. However, conductivity probes the overall scattering rate, so a dominant channel associated with long-range Coulomb scattering will mask weaker short-range channels. We present weak localization measurements of epitaxial graphene with lithium adatoms that separately quantify intra- and intervalley scattering rates, then compare the measurements to tight-binding calculation…
Fluorine adatoms on graphene induce local changes in electronic and magnetic properties, and subtle correlation effects. We investigate the GGA and GGA+U approaches as possible solutions to describe the magnetic moment and electronic band structure of graphene sheets with fluorine adatoms, and compare to experiments. We show that, due to a lack of strong electronic correlations, GGA fails to reproduce the measured magnetic moment in this structure. In particular, the GGA incorrectly predicts a nonmagnetic ground state with a zero band gap. On the other hand, GGA+U is a computationally efficien…
We study the spectral function and quasiparticle scattering in Li-decorated graphene (Li@graphene) with an atomistic $T$-matrix formalism and uncover adatom-induced spectral effects which shed light on experimentally observed angle-resolved photoemission spectroscopy (ARPES) features. From transport studies, alkali adatoms are known to introduce charged-impurity scattering limiting the carrier mobility. Here, we demonstrate that Li adatoms furthermore give rise to a low-energy impurity band centered at the $Γ$ point which originates from the hybridization between the atomic 2s state of the Li …
The spin dynamics of the strongly localized, donor-bound electrons in fluorine-doped ZnSe epilayers is studied by pump-probe Kerr rotation techniques. A method exploiting the spin inertia is developed and used to measure the longitudinal spin relaxation time, $T_1$, in a wide range of magnetic fields, temperatures, and pump densities. The $T_1$ time of the donor-bound electron spin of about 1.6 $μ$s remains nearly constant for external magnetic fields varied from zero up to 2.5 T (Faraday geometry) and in a temperature range $1.8-45$ K. The inhomogeneous spin dephasing time, $T_2^*=8-33$ ns, i…
We report the experimental observation of sublattice-resolved resonant scattering in bilayer graphene by performing simultaneous cryogenic atomic hydrogen doping and electron transport measurements in ultrahigh vacuum. This allows us to monitor the hydrogen adsorption on the different sublattices of bilayer graphene without atomic-scale microscopy. Specifically, we detect two distinct resonant scattering peaks in the gate-dependent resistance, which evolve as a function of atomic hydrogen dosage. Theoretical calculations show that one of the peaks originates from resonant scattering by hydroge…
The electronic transport of monolayer graphene devices is studied before and after \emph{in situ} deposition of a sub-monolayer coating of osmium adatoms. Unexpectedly, and unlike all other metallic adatoms studied to date, osmium adatoms shift the charge neutrality point to more positive gate voltages. This indicates that osmium adatoms act as electron acceptors and thus leave the graphene hole-doped. Analysis of transport data suggest that Os adatoms behave as charged impurity scatterers, albeit with a surprisingly low charge-doping efficiency. The charge neutrality point of graphene is foun…
The issue of whether local magnetic moments can be formed by introducing adatoms into graphene is of intense research interest because it opens the window to fundamental studies of magnetism in graphene, as well as of its potential spintronics applications. To investigate this question we measure, by exploiting the well-established weak localization physics, the phase coherence length L_phi in dilute fluorinated graphene. L_phi reveals an unusual saturation below ~ 10 K, which cannot be explained by non-magnetic origins. The corresponding phase breaking rate increases with decreasing carrier d…
The feature-rich electronic and magnetic properties of fluorine-doped graphene nanoribbons are investigated by the first-principles calculations. They arise from the cooperative or competitive relations among the significant chemical bonds, finite-size quantum confinement and edge structure. There exist C-C, C-F, and F-F bonds with the multi-orbital hybridizations. Fluorine adatoms can create the p-type metals or the concentration- and distribution-dependent semiconductors, depending on whether the $π$ bonding is seriously suppressed by the top-site chemical bonding. Furthermore, five kinds of…
We have investigated the way in which the concentration and distribution of adatoms affect the geometric and electronic properties of graphene. Our calculations were based on the use of first principle under the density functional theory which reveal various types of $π$-bonding. The energy band structure of this doped graphene material may be explored experimentally by employing angle-resolved photo-emission spectroscopy (ARPES) for electronic band structure measurements and scanning tunneling spectroscopy (STS) for the density-of-states (DOS) both of which have been calculated and reported i…
We perform a comparative study of the spin relaxation by spin-orbit coupling induced from adatoms (hydrogen and fluorine) in graphene. Two methods are applied, giving consistent results: a full quantum transport simulation of a graphene nanoribbon, and a T-matrix calculation using Green's functions for a single adatom in graphene. For hydrogenated graphene the dominant spin-orbit term for spin relaxation is PIA, the hitherto neglected interaction due to pseudospin inversion asymmetry. In contrast, in fluorinated graphene PIA and Rashba couplings destructively interfere, reducing the total spin…
Based on the results of first-principles calculations we demonstrate that significant distortion of graphene sheets caused by adsorption of fluorine atoms leads to the formation of metastable patterns for which the next step of fluorination is considerably less energetically favorable. Existence of these stable patterns oriented along the armchair direction makes possible the synthesis of various CFx structures. The combination of strong distortion of the nonfluorinated graphene sheet with the doping caused by the polar nature of C-F bonds reduces the energy cost of migration and the energy of…
We study the electronic structure of diluted F atoms chemisorbed on graphene using density functional theory calculations. We show that the nature of the chemical bonding of a F atom adsorbed on top of a C atom in graphene strongly depends on carrier doping. In neutral samples the F impurities induce a sp^3-like bonding of the C atom below, generating a local distortion of the hexagonal lattice. As the graphene is electron-doped, the C atom retracts back to the graphene plane and for high doping (10^14 cm^-2) its electronic structure corresponds to a nearly pure sp^2 configuration. We interpre…
This work presents a systematic review of the feature-rich essential properties in graphene-related systems using the first-principles method. The geometric and electronic properties are greatly diversified by the number of layers, the stacking configurations, the sliding-created configuration transformation, the rippled structures, and the distinct adatom adsorptions. The top-site adsorptions can induce the significantly buckled structures, especially for hydrogen and fluorine adatoms. The electronic structures consist of the carbon-, adatom- and (carbon, adatom)-dominated energy bands. There…
Using magnetization measurements, we show that point defects in graphene - fluorine adatoms and irradiation defects (vacancies) - carry magnetic moments with spin 1/2. Both types of defects lead to notable paramagnetism but no magnetic ordering could be detected down to liquid helium temperatures. The induced paramagnetism dominates graphene's low-temperature magnetic properties despite the fact that maximum response we could achieve was limited to one moment per approximately 1000 carbon atoms. This limitation is explained by clustering of adatoms and, for the case of vacancies, by losing gra…
The electron-transport properties of adatom-graphene system are investigated for different (random, correlated, and ordered) spatial configurations of adatoms over different types of high symmetry sites with various adsorption heights. K adatoms in monolayer graphene are modeled by the scattering potential adapted from the independent self-consistent ab initio calculations. The results are obtained numerically using the quantum-mechanical Kubo-Greenwood formalism. A band gap may be opened only if ordered adatoms act as substitutional atoms, while there is no band gap opening for adatoms acting…
We study ballistic transport properties of graphene with a low concentration of vacancies or adatoms. The conductance of graphene doped to the Dirac point is found to depend on the relative distribution of impurities among different sites of the honeycomb lattice labeled in general by six colors. The conductivity is shown to be sensitive to the crystal orientation if adatom sites have a preferred color. Our theory is confirmed by numerical simulations using recursive Green's functions with no adjustable parameters.
The electronic properties of aluminum-doped graphenes enriched by multi-orbital hybridizations are investigated using first-principles calculations. The feature-rich electronic structures exhibit the quasi-rigid red shifts of the carbon-created energy bands, the Al-dominated valence and conduction bands, and many free electrons in the conduction Dirac cone. These are directly reflected in the special structures of density of states (DOS). The Al- and alkali-induced high free carrier densities are almost the same. There exist certain important differences among the Al-, alkali- and halogen-dope…
We consider a dilute fluorinated graphene nanoribbon as a spin-active element. The fluorine adatoms introduce a local spin-orbit Rashba interaction that induces spin-precession for electron passing by. In the absence of the external magnetic field the transport is dominated by multiple scattering by adatoms which cancels the spin precession effects, since the direction of the spin precession depends on the electron momentum. Accumulation of the spin precession effects is possible provided that the Fermi level electron passes many times near the same adatom with the same momentum. In order to a…
Enhancement of the chemical activity of graphene is evidenced by first-principles modelling of chemisorption of the hydrogen, fluorine, oxygen and hydroxyl groups on strained graphene. For the case of negative strain or compression, chemisorption of the single hydrogen, fluorine or hydroxyl group is energetically more favourable than those of their pairs on different sublattices. This behaviour stabilizes the magnetism caused by the chemisorption being against its destruction by the pair formations. Initially flat, compressed graphene is shown to buckle spontaneously right after chemisorption …
We theoretically investigate spin-resolved currents flowing in large-area graphene, with and without defects, doped with single atoms of noble metals (Cu, Ag and Au) and 3d-transition metals (Mn,Fe,Co and Ni). We show that the presence of a local magnetic moment is a necessary but not sufficient condition to have a non zero current polarization. An essential requirement is the presence of spin-split localized levels near the Fermi energy that strongly hybridize with the graphene pi-bands. We also show that a gate potential can be used to tune the energy of these localized levels, leading to an…
Inducing a robust long-range magnetic order in diamagnetic graphene remains a challenge. While nitrogen-doped graphene is reported to be a promising candidate, the corresponding exchange mechanism endures unclear and is essential to tune further and manipulate magnetism. Within the first-principles calculations, we systematically investigate the local moment formation and the concurrent interaction between various defect complexes. The importance of adatom diffusion on the differential defect abundance is discussed. The individual nitrogen complexes that contribute toward itinerant and a local…
The significant halogenation effects on the essential properties of graphene are investigated by the first-principles method. The geometric structures, electronic properties, and magnetic configurations are greatly diversified under the various halogen adsorptions. Fluorination, with the strong multi-orbital chemical bondings, can create the buckled graphene structure, while the other halogenations do not change the planar σ bonding in the presence of single-orbital hybridization. Electronic structures consist of the carbon-, adatom- and (carbon, adatom)-dominated energy bands. All halogenated…
Adsorbed atoms and molecules play an important role in controlling and tuning the functional properties of two-dimensional (2D) materials. Understanding and predicting this process from theory is challenging because of the need to capture the complex interplay between the local chemistry and the long-range screening response. To address this problem, we present a first-principles multiscale approach that combines linear-scaling density-functional theory, continuum screening theory and large-scale tight-binding simulations into a seamless parameter-free theory of adsorbates on 2D materials. We …
It has been shown that the first C layer on the SiC(0001)(2{\times}2)C surface already exhibits graphene-like electronic structure, with linear pi bands near the Dirac point. Indeed, the (2{\times}2)C reconstruction, with a Si adatom and C restatom structure, efficiently passivates the SiC(0001) surface thanks to an adatom/restatom charge transfer mechanism. Here, we study the effects of interface modifications on the graphene layer using density functional theory calculations. The modifications we consider are inspired from native interface defects observed by scanning tunneling microscopy. O…
Graphene phonons are measured as a function of electron doping via the addition of potassium adatoms. In the low doping regime, the in-plane carbon G-peak hardens and narrows with increasing doping, analogous to the trend seen in graphene doped via the field-effect. At high dopings, beyond those accessible by the field-effect, the G-peak strongly softens and broadens. This is interpreted as a dynamic, non-adiabatic renormalization of the phonon self-energy. At dopings between the light and heavily doped regimes, we find a robust inhomogeneous phase where the potassium coverage is segregated in…
The Kondo effect in the system consisting of a magnetic adatom on the graphene is studied. By using the non-equilibrium Green function method with the slave-boson mean field approximation, the local density of state (LDOS) and the conductance are calculated. For a doped graphene, the Kondo phase is present at all time. Surprisingly, two kinds of Kondo regimes are revealed. But for the undoped graphene, the Kondo phase only exists if the adatom's energy level is beyond a critical value. The conductance is similar to the LDOS, thus, the Kondo peak in the LDOS can be observed with the scanning tu…
