Mechanisms of molecular doping of graphene: A first-principles study

Doping graphene with electron donating or accepting molecules is an interesting approach to introduce carriers into it, analogous to electrochemical doping accomplished in graphene when used in a field-effect transistor. Here, we use first-principles density-functional theory to determine changes in the electronic-structure and vibrational properties of graphene that arise from the adsorption of aromatic molecules such as aniline and nitrobenzene. Identifying the roles of various mechanisms of chemical interaction between graphene and a molecule, we bring out the contrast between electrochemical and molecular doping of graphene. Our estimates of various contributions to shifts in the Raman-active modes of graphene with molecular doping are fundamental to the possible use of Raman spectroscopy in (a) characterization of the nature and concentration of carriers in graphene with molecular doping, and (b) graphene-based chemical sensors.

Femtosecond carrier dynamics and saturable absorption in graphene suspensions

Nonlinear optical properties and carrier relaxation dynamics in graphene, suspended in three different solvents, are investigated using femtosecond (80 fs pulses) Z-scan and degenerate pump-probe spectroscopy at 790 nm. The results demonstrate saturable absorption property of graphene with a nonlinear absorption coefficient, beta of (similar to 2-9) x 10(-8) cm/W. Two distinct time scales associated with the relaxation of photoexcited carriers, a fast one in the range of 130-330 fs (related to carrier-carrier scattering) followed by it slower one in 3.5-4.9 ps range (associated with carrier-phonon scattering) are observed. (C) 2009 American Institute of Physics.

Synthesis, Structure, and Properties of Boron- and Nitrogen-Doped Graphene

Boron- and nitrogen-doped graphenes are are prepared by the arc discharge between carbon electrodes or by the transformation of nanodiamond under appropriate atmospheres. Using a combination of experiment and theories based on first principles, systematic changes in the carrier-concentration and electronic structure of the doped graphenes are demonstrated. Stiffening of the G-band mode and intensification of the defect-related D-band in the Raman spectra are also observed.

BCN:A Graphene Analogue with Remarkable Adsorptive Properties

A new analogue of graphene containing boron, carbon and nitrogen (BCN) has been obtained by the reaction of high-surface-area activated charcoal with a mixture of boric acid and urea at 900 degrees C. X-ray photoelectron spectroscopy and electron energy-loss spectroscopy reveal the composition to be close to BCN. The X-ray diffraction pattern, high-resolution electron microscopy images and Raman spectrum indicate the presence of graphite-type layers with low sheet-to-sheet registry. Atomic force microscopy reveals the sample to consist of two to three layers of BCN, as in a few-layer graphene. BCN exhibits more electrical resistivity than graphene, but weaker magnetic features. BCN exhibits a surface area of 2911 m(2)g(-1), which is the highest value known for a BxCyNz composition. It exhibits high propensity for adsorbing CO2 (approximate to 100 wt %) at 195 K and a hydrogen uptake of 2.6 wt % at 77 K. A first-principles pseudopotential-based DFT study shows the stable structure to consist of BN3 and NB3 motifs. The calculations also suggest the strongest CO2 adsorption to occur with a binding energy of 3.7 kJ mol(-1) compared with 2.0 kJ mol(-1) on graphene.

Possible high-temperature superconducting state with a d plus id pairing symmetry in doped graphene

Motivated by a suggestion in our earlier work [G. Baskaran, Phys. Rev. B 65, 212505 (2002)], we study electron correlation driven superconductivity in doped graphene where on-site correlations are believed to be of intermediate strength. Using an extensive variational Monte Carlo study of the repulsive Hubbard model and a correlated ground state wave function, we show that doped graphene supports a superconducting ground state with a d+id pairing symmetry. We estimate superconductivity reaching room temperatures at an optimal doping of about 15%-20%. Our work suggests that correlations can stabilize superconductivity even in systems with intermediate coupling.

Graphene Analogues of BN: Novel Synthesis and Properties

Enthused by the fascinating properties of graphene, we have prepared graphene analogues of BN by a chemical method with a control on the number of layers. The method involves the reaction of boric acid with urea, wherein the relative proportions of the two have been varied over a wide range. Synthesis with a high proportion of urea yields a product with a majority of 1-4 layers. The surface area of BN increases progressively with the decreasing number of layers, and the high surface area BN exhibits high CO, adsorption, but negligible H, adsorption. Few-layer BN has been solubilized by interaction with Lewis bases. We have used first-principles simulations to determine structure, phonon dispersion, and elastic properties of BN with planar honeycomb lattice-based n-layer forms. We find that the mechanical stability of BN with respect to out-of-plane deformation is quite different from that of graphene, as evident in the dispersion of their flexural modes. BN is softer than graphene and exhibits signatures of long-range ionic interactions in its optical phonons. Finally, structures with different stacking sequences of BN have comparable energies, suggesting relative abundance of slip faults, stacking faults, and structural inhomogeneities in multilayer BN.

Intrinsic limits of subthreshold slope in biased bilayer graphene transistor

In this work, we investigate the intrinsic limits of subthreshold slope in a dual gated bilayer graphene transistor using a coupled self-consistent Poisson-bandstructure solver. We benchmark the solver by matching the bias dependent band gap results obtained from the solver against published experimental data. We show that the intrinsic bias dependence of the electronic structure and the self-consistent electrostatics limit the subthreshold slope obtained in such a transistor well above the Boltzmann limit of 60 mV/decade at room temperature, but much below the results experimentally shown till date, indicating room for technological improvement of bilayer graphene.

Some Novel Attributes of Graphene

Graphene has generated, great sensation due to its amazing properties,and extensive research is being pursued on single as well as bi- and few-layer graphenes. In this Perspective, we highlight some aspects of graphene synthesis surface, magnetic, and mechanical properties, as well as effects of doping and indicate a few useful directions for future research.

Anisotropy of the Stone-Wales defect and warping of graphene nanoribbons: A first-principles analysis

Stone-Wales (SW) defects, analogous to dislocations in crystals, play an important role in mechanical behavior of sp(2)-bonded carbon based materials. Here, we show using first-principles calculations that a marked anisotropy in the interaction among the SW defects has interesting consequences when such defects are present near the edges of a graphene nanoribbon: depending on their orientation with respect to edge, they result in compressive or tensile stress, and the former is responsible to depression or warping of the graphene nanoribbon. Such warping results in delocalization of electrons in the defect states.

Negative differential conductance and effective electron mass in highly asymmetric ballistic bilayer graphene nanoribbon

We present a simplified theory of the effective momentum mass (EMM) and ballistic current–voltage relationship in a degenerate two-folded highly asymmetric bilayer graphene nanoribbon. With an increase in the gap, the density-of-states in the lower set of subbands increases more than that of the upper set. This results in a phenomenological population inversion of carriers, which is reflected through a net negative differential conductance (NDC). It is found that with the increase of the ribbon width, the NDC also increases. The population inversion also signatures negative values of EMM above a certain ribbon-width for the lower set of subbands, which increases in a step-like manner with the applied longitudinal static bias. The well-known result for symmetric conditions has been obtained as a special case.

Probing top-gated field effect transistor of reduced graphene oxide monolayer made by dielectrophoresis

We demonstrate a top-gated field effect transistor made of a reduced graphene oxide (RGO) monolayer (graphene) by dielectrophoresis. The Raman spectrum of RGO flakes of typical size of 5 mu m x 5 mu m shows a single 2D band at 2687 cm(-1), characteristic of single-layer graphene.The two-probe current-voltage measurements of RGO flakes, deposited in between the patterned electrodes with a gap of 2.5 mu m using ac dielectrophoresis, show ohmic behavior with a resistance of similar to 37 k Omega. The temperature dependence of the resistance (R) of RGO measured between 305 K and 393 K yields a temperature coefficient of resistance [dR/dT]/R similar to -9.5 x 10(-4)/K, the same as that of mechanically exfoliated single-layer graphene. The field-effect transistor action was obtained by electrochemical top-gating using a solid polymer electrolyte (PEO + LiClO4) and Pt wire. The ambipolar nature of graphene flakes is observed up to a doping level of similar to 6 x 10(12)/cm(2) and carrier mobility of similar to 50 cm(2)/V s. The source-drain current characteristics show a tendency of current saturation at high source-drain voltage which is analyzed quantitatively by a diffusive transport model. (C) 2010 Elsevier Ltd. All rights reserved.

External Bias Dependent Direct To Indirect Band Gap Transition in Graphene Nanoribbon

In this work, using self-consistent tight-binding calculations. for the first time, we show that a direct to indirect band gap transition is possible in an armchair graphene nanoribbon by the application of an external bias along the width of the ribbon, opening up the possibility of new device applications. With the help of the Dirac equation, we qualitatively explain this band gap transition using the asymmetry in the spatial distribution of the perturbation potential produced inside the nanoribbon by the external bias. This is followed by the verification of the band gap trends with a numerical technique using Magnus expansion of matrix exponentials. Finally, we show that the carrier effective masses possess tunable sharp characters in the vicinity of the band gap transition points.

Investigation of the effect of nonlocal scale on ultrasonic wave dispersion characteristics of a monolayer graphene

In this article, an ultrasonic wave propagation in graphene sheet is studied using nonlocal elasticity theory incorporating small scale effects. The graphene sheet is modeled as an isotropic plate of one-atom thick. For this model, the nonlocal governing differential equations of motion are derived from the minimization of the total potential energy of the entire system. An ultrasonic type of wave propagation model is also derived for the graphene sheet. The nonlocal scale parameter introduces certain band gap region in in-plane and flexural wave modes where no wave propagation occurs. This is manifested in the wavenumber plots as the region where the wavenumber tends to infinite or wave speed tends to zero. The frequency at which this phenomenon occurs is called the escape frequency. The explicit expressions for cutoff frequencies and escape frequencies are derived. The escape frequencies are mainly introduced because of the nonlocal elasticity. Obviously these frequencies are function of nonlocal scaling parameter. It has also been obtained that these frequencies are independent of y-directional wavenumber. It means that for any type of nanostructure, the escape frequencies are purely a function of nonlocal scaling parameter only. It is also independent of the geometry of the structure. It has been found that the cutoff frequencies are function of nonlocal scaling parameter (e(0)a) and the y-directional wavenumber (k(y)). For a given nanostructure, nonlocal small scale coefficient can be obtained by matching the results from molecular dynamics (MD) simulations and the nonlocal elasticity calculations. At that value of the nonlocal scale coefficient, the waves will propagate in the nanostructure at that cut-off frequency. In the present paper, different values of e(o)a are used. One can get the exact e(0)a for a given graphene sheet by matching the MD simulation results of graphene with the results presented in this paper. (C) 2010 Elsevier B.V. All rights reserved.

XPS evidence for molecular charge-transfer doping of graphene

By employing X-ray photoelectron spectroscopy (XPS), we have been able to establish the occurrence of charge-transfer doping in few-layer graphene covered with electron acceptor (TCNE) and donor (TTF) molecules. We have performed quantitative estimates of the extent of charge transfer in these complexes and elucidated the origin of unusual shifts of their Raman G-bands and explained the differences in the dependence of conductivity on n- and p-doping. The study unravels the cause of the apparent difference between the charge-transfer doping and electrochemical doping. (C) 2010 Elsevier B.V. All rights reserved.

Graphene analogue BCN: Femtosecond nonlinear optical susceptibility and hot carrier dynamics

Third-order nonlinear absorption and refraction coefficients of a few-layer boron carbon nitride (BCN) and reduced graphene oxide (RGO) suspensions have been measured at 3.2 eV in the femtosecond regime. Optical limiting behavior is exhibited by BCN as compared to saturable absorption in RGO. Nondegenerate time-resolved differential transmissions from BCN and RGO show different relaxation times. These differences in the optical nonlinearity and carrier dynamics are discussed in the light of semiconducting electronic band structure of BCN vis-a-vis the Dirac linear band structure of graphene. (C) 2010 Elsevier B.V. All rights reserved.