Aharonov-Bohm interferences in polycrystalline graphene.

Aharonov-Bohm (AB) interferences in the quantum Hall regime can be achieved, provided that electrons are able to transmit between two edge channels in nanostructures. Pioneering approaches include quantum point contacts in 2DEG systems, bipolar graphene p-n junctions, and magnetic field heterostructures. In this work, defect scattering is proposed as an alternative mechanism to achieve AB interferences in polycrystalline graphene. Indeed, due to such scattering, the extended defects across the sample can act as tunneling paths connecting quantum Hall edge channels. Consequently, strong AB oscillations in the conductance are predicted in polycrystalline graphene systems with two parallel grain boundaries. In addition, this general approach is demonstrated to be applicable to nano-systems containing two graphene barriers with functional impurities and perspectively, can also be extended to similar systems of 2D materials beyond graphene.

Valley Filtering and Electronic Optics Using Polycrystalline Graphene.

In this Letter, both the manipulation of valley-polarized currents and the optical-like behaviors of Dirac fermions are theoretically explored in polycrystalline graphene. When strain is applied, the misorientation between two graphene domains separated by a grain boundary can result in a mismatch of their electronic structures. Such a discrepancy manifests itself in a strong breaking of the inversion symmetry, leading to perfect valley polarization in a wide range of transmission directions. In addition, these graphene domains act as different media for electron waves, offering the possibility to modulate and obtain negative refraction indexes.

Transport properties through graphene grain boundaries: strain effects versus lattice symmetry.

As most materials available at the macroscopic scale, graphene samples usually appear in a polycrystalline form and thus contain grain boundaries. In the present work, the effect of uniaxial strain on the electronic transport properties through graphene grain boundaries is investigated using atomistic simulations. A systematic picture of transport properties with respect to the strain and lattice symmetry of graphene domains on both sides of the boundary is provided. In particular, it is shown that strain engineering can be used to open a finite transport gap in all graphene systems where the two domains are arranged in different orientations. This gap value is found to depend on the strain magnitude, on the strain direction and on the lattice symmetry of graphene domains. By choosing appropriately the strain direction, a large transport gap of a few hundred meV can be achieved when applying a small strain of only a few percents. For a specific class of graphene grain boundary systems, strain engineering can also be used to reduce the scattering on defects and thus to significantly enhance the conductance. With a large strain-induced gap, these graphene heterostructures are proposed to be promising candidates for highly sensitive strain sensors, flexible electronic devices and p-n junctions with non-linear I-V characteristics.

Atypical Exciton-Phonon Interactions in WS2 and WSe2 Monolayers Revealed by Resonance Raman Spectroscopy.

Resonant Raman spectroscopy is a powerful tool for providing information about excitons and exciton-phonon coupling in two-dimensional materials. We present here resonant Raman experiments of single-layered WS2 and WSe2 using more than 25 laser lines. The Raman excitation profiles of both materials show unexpected differences. All Raman features of WS2 monolayers are enhanced by the first-optical excitations (with an asymmetric response for the spin-orbit related XA and XB excitons), whereas Raman bands of WSe2 are not enhanced at XA/B energies. Such an intriguing phenomenon is addressed by DFT calculations and by solving the Bethe-Salpeter equation. These two materials are very similar. They prefer the same crystal arrangement, and their electronic structure is akin, with comparable spin-orbit coupling. However, we reveal that WS2 and WSe2 exhibit quite different exciton-phonon interactions. In this sense, we demonstrate that the interaction between XC and XA excitons with phonons explains the different Raman responses of WS2 and WSe2, and the absence of Raman enhancement for the WSe2 modes at XA/B energies. These results reveal unusual exciton-phonon interactions and open new avenues for understanding the two-dimensional materials physics, where weak interactions play a key role coupling different degrees of freedom (spin, optic, and electronic).

Strain-induced metal-semiconductor transition observed in atomic carbon chains.

Carbyne, the sp(1)-hybridized phase of carbon, is still a missing link in the family of carbon allotropes. While the bulk phases of carbyne remain elusive, the elementary constituents, that is, linear chains of carbon atoms, have already been observed using the electron microscope. Isolated atomic chains are highly interesting one-dimensional conductors that have stimulated considerable theoretical work. Experimental information, however, is still very limited. Here we show electrical measurements and first-principles transport calculations on monoatomic carbon chains. When the 1D system is under strain, the chains are semiconducting corresponding to the polyyne structure with alternating bond lengths. Conversely, when the chain is unstrained, the ohmic behaviour of metallic cumulene with uniform bond lengths is observed. This confirms the recent prediction of a metal-insulator transition that is induced by strain. The key role of the contacting leads explains the rectifying behaviour measured in monoatomic carbon chains in a nonsymmetric contact configuration.

Spin filtering and magneto-resistive effect at the graphene/h-BN ribbon interface.

Advances in the realization of hybrid graphene/h-BN materials open new ways to control the electronic properties of graphene nanostructures. In this paper, the structural, electronic, and transport properties of heterojunctions made of bare zigzag-shaped h-BN and graphene ribbons are investigated using first-principles techniques. Our results highlight the potential of graphene/h-BN junctions for applications in spintronic devices. At first, density functional theory is used to detail the role played by the edge states and dangling bonds in the electronic and magnetic behavior of h-BN and graphene ribbons. Then, the electronic conductance of the junction is computed in the framework of Green's function-based scattering theory. In its high-spin configuration, the junction reveals a full spin polarization of the propagating carriers around the Fermi energy, and the magnitude of the transmission probability is predicted to be strongly dependent on the relative orientation of magnetic momenta in the leads.

Single-molecule sensing using carbon nanotubes decorated with magnetic clusters.

First-principles and nonequilibrium Green's function techniques are used to investigate magnetism and spin-polarized quantum transport in metallic carbon nanotubes (CNT) decorated with transition metal (Ni(13), Pt(13)) magnetic nanoclusters (NC). For small cluster sizes, the strong CNT-NC interaction induces spin-polarization in the CNT. The adsorption of a benzene molecule is found to drastically modify the CNT-NC magnetization. Such a magnetization change should be large enough to be detected via magnetic-AFM or SQUID magnetometry, hence suggesting a novel approach for single-molecule gas detection.

One-dimensional extended lines of divacancy defects in graphene.

Since the outstanding transport properties of graphene originate from its specific structure, modification at the atomic level of the graphene lattice is needed in order to change its electronic properties. Thus, topological defects play an important role in graphene and related structures. In this work, one-dimensional (1D) arrangement of topological defects in graphene are investigated within a density functional theory framework. These 1D extended lines of pentagons, heptagons and octagons are found to arise either from the reconstruction of divacancies, or from the epitaxial growth of graphene. The energetic stability and the electronic structure of different ideal extended lines of defects are calculated using a first-principles approach. Ab initio scanning tunneling microscopy (STM) images are predicted and compared to recent experiments on epitaxial graphene. Finally, local density of states and quantum transport calculations reveal that these extended lines of defects behave as quasi-1D metallic wires, suggesting their possible role as reactive tracks to anchor molecules or atoms for chemical or sensing applications.

Quantum spin transport in carbon chains.

First-principles and non-equilibrium Green's function approaches are used to predict spin-polarized electronic transport in monatomic carbon chains covalently connected to graphene nanoribbons, as recently synthetized experimentally (Jin, C.; et al. Phys. Rev. Lett. 2009, 102, 205501-205504). Quantum electron conductances exhibit narrow resonant states resulting from the simultaneous presence of open conductance channels in the contact region and on the chain atoms. Odd-numbered chains, which acquire metallic or semiconducting character depending on the nature of the edge at the graphene contact, always display a net spin polarization. The combination of electrical and magnetic properties of chains and contacts results in nanodevices with intriguing spintronic properties such as the coexistence of magnetic and semiconducting behaviors.

Carbon nanotubes randomly decorated with gold clusters: from nano2hybrid atomic structures to gas sensing prototypes.

Carbon nanotube surfaces, activated and randomly decorated with metal nanoclusters, have been studied in uniquely combined theoretical and experimental approaches as prototypes for molecular recognition. The key concept is to shape metallic clusters that donate or accept a fractional charge upon adsorption of a target molecule, and modify the electron transport in the nanotube. The present work focuses on a simple system, carbon nanotubes with gold clusters. The nature of the gold-nanotube interaction is studied using first-principles techniques. The numerical simulations predict the binding and diffusion energies of gold atoms at the tube surface, including realistic atomic models for defects potentially present at the nanotube surface. The atomic structure of the gold nanoclusters and their effect on the intrinsic electronic quantum transport properties of the nanotube are also predicted. Experimentally, multi-wall CNTs are decorated with gold clusters using (1) vacuum evaporation, after activation with an RF oxygen plasma and (2) colloid solution injected into an RF atmospheric plasma; the hybrid systems are accurately characterized using XPS and TEM techniques. The response of gas sensors based on these nano(2)hybrids is quantified for the detection of toxic species like NO(2), CO, C(2)H(5)OH and C(2)H(4).

Experimental and theoretical studies suggesting the possibility of metallic boron nitride edges in porous nanourchins.

We first describe the synthesis of novel and highly porous boron nitride (BN) nanospheres (100-400 nm o.d.) that exhibit a rough surface consisting of open BN nanocones and corrugated BN ribbons. The material was produced by reacting B2O3 with nanoporous carbon spheres under nitrogen at ca. 1750 degrees C. The BN nanospheres were characterized using scanning electron microscopy, high-resolution electron microscopy, and electron energy loss spectroscopy. The porous BN spheres show relatively large surface areas of ca. 290 m2/g and exhibit surprisingly stable field emission properties at low turn-on voltages (e.g., 1-1.3 V/microm). We attribute these outstanding electron emission properties to the presence of finite BN ribbons located at the surface of the nanospheres (exhibiting zigzag edges), which behave like metals as confirmed by first-principles calculations. In addition, our ab initio theoretical results indicate that the work function associated to these zigzag BN ribbons is 1.3 eV lower when compared with BN-bulk material.

Catalytically assisted tip growth mechanism for single-wall carbon nanotubes.

The catalytic growth of single-wall carbon nanotubes is investigated at the nanotube tip using first-principles molecular dynamics and tight-binding Monte Carlo simulations. At experimental temperatures (approximately 1500 K), the catalytic atom is found to incorporate into the carbon network instead of scooting around the open edge. Consequently, the open end of SWNTs closes spontaneously into a graphitic dome, suggesting a closed-end mechanism for the catalytic growth. At 1500 K, the cobalt-carbon chemical bonds keep breaking and re-forming, providing a direct incorporation process for additional carbon, necessary for growth. The catalytic action of Co atoms is also found to play a key role in the reconstruction of the nanotube tip after carbon incorporation, by annealing defects. The present closed-end tip growth mechanism may coexist with the usual root growth mechanism.

Room temperature peierls distortion in small diameter nanotubes.

By means of ab initio simulations, we investigate the phonon band structure and electron-phonon coupling in small 4-A diameter nanotubes. We show that both the C(5,0) and C(3,3) tubes undergo above room temperature a Peierls transition mediated by an acoustical long wavelength and an optical q=2k(F) phonon, respectively. In the armchair geometry, we verify that the electron-phonon coupling parameter lambda originates mainly from phonons at q=2k(F) and is strongly enhanced when the diameter decreases. These results question the origin of superconductivity in small diameter nanotubes.

Defects in carbon nanotubes.

Carbon nanotubes are quasi one-dimensional nanostructures with unique eletrical prroperties that make them prime candidates for molecular electronics, which is certainly a most promising direction in nanotechnology. Early theoretical works predicted that the electronic properties of "ideal" carbon nanotubes depend on their diameter and chirality. However, carbon nanotubes are probably not as perfect as they were once thought to be. Defects such as pentagons, heptagons, vacancies, or dopant are found to modify drastically the electronic properties of these nanosystems. Irradiation processes can lead to interesting, highly defective nanostructures and also to the coalescence of nanotubes within a rope. The introduction of defects in the carbon network is thus an interesting way to tailor its intrinsic properties, to create new potential nanodevices. The aim of the present Acount is to investigate theoretically the effects of different types of defects on the electronic properties of carbon nanotubes, and to propose new potential applications in nanoelectronics.

Molecular junctions by joining single-walled carbon nanotubes.

Crossing single-walled carbon nanotubes can be joined by electron beam welding to form molecular junctions. Stable junctions of various geometries are created in situ in a transmission electron microscope. Electron beam exposure at high temperatures induces structural defects which promote the joining of tubes via cross-linking of dangling bonds. The observations are supported by molecular dynamics simulations which show that the creation of vacancies and interstitials induces the formation of junctions involving seven- or eight-membered carbon rings at the surface between the tubes.

New metallic allotropes of planar and tubular carbon

We propose a new family of layered sp(2)-like carbon crystals, incorporating five-, six-, and seven-membered rings in 2D Bravais lattices. These periodic sheets can be rolled so as to generate nanotubes of different diameter and chirality. We demonstrate that these sheets and tubes are metastable and more favorable than C60, and it is also shown that their mechanical properties are similar to those of graphene. Density of states calculations of all structures revealed an intrinsic metallic behavior, independent of orientation, tube diameter, and chirality.

Microscopic Growth Mechanisms for Carbon Nanotubes

The uncatalyzed edge growth of carbon nanotubes was investigated by first-principles molecular dynamics simulations. At experimental temperatures the open end of single-walled nanotubes closed spontaneously into a graphitic dome, which may explain why these nanotubes do not grow in the absence of transition metal catalysts. On the other hand, chemical bonding between the edges of adjacent coaxial tubes ("lip-lip" interactions) trapped the end of a double-walled nanotube in a metastable energy minimum, thus preventing dome closure. These calculations show that this end geometry exhibits a high degree of chemical activity and easily accommodates incoming carbon fragments, supporting a model of growth by chemisorption from the vapor phase.