Electronic and optical properties of strained graphene and other strained 2D materials: a review.

This review presents the state of the art in strain and ripple-induced effects on the electronic and optical properties of graphene. It starts by providing the crystallographic description of mechanical deformations, as well as the diffraction pattern for different kinds of representative deformation fields. Then, the focus turns to the unique elastic properties of graphene, and to how strain is produced. Thereafter, various theoretical approaches used to study the electronic properties of strained graphene are examined, discussing the advantages of each. These approaches provide a platform to describe exotic properties, such as a fractal spectrum related with quasicrystals, a mixed Dirac-Schrödinger behavior, emergent gravity, topological insulator states, in molecular graphene and other 2D discrete lattices. The physical consequences of strain on the optical properties are reviewed next, with a focus on the Raman spectrum. At the same time, recent advances to tune the optical conductivity of graphene by strain engineering are given, which open new paths in device applications. Finally, a brief review of strain effects in multilayered graphene and other promising 2D materials like silicene and materials based on other group-IV elements, phosphorene, dichalcogenide- and monochalcogenide-monolayers is presented, with a brief discussion of interplays among strain, thermal effects, and illumination in the latter material family.

Excited excitonic states in 1L, 2L, 3L, and bulk WSe2 observed by resonant Raman spectroscopy.

Resonant Raman spectroscopy (RRS) is a very useful tool to study physical properties of materials since it provides information about excitons and their coupling with phonons. We present in this work a RRS study of samples of WSe2 with one, two, and three layers (1L, 2L, and 3L), as well as bulk 2H-WSe2, using up to 20 different laser lines covering the visible range. The first- and second-order Raman features exhibit different resonant behavior, in agreement with the double (and triple) resonance mechanism(s). From the laser energy dependence of the Raman intensities (Raman excitation profile, or REP), we obtained the energies of the excited excitonic states and their dependence with the number of atomic layers. Our results show that Raman enhancement is much stronger for the excited A' and B' states, and this result is ascribed to the different exciton-phonon coupling with fundamental and excited excitonic states.

Analysis of the molecular structure of human enamel with fluorosis using micro-Raman spectroscopy.

The aim of this study was to analyze the molecular structure of enamel with fluorosis using micro-Raman spectroscopy and compare it with that of healthy enamel. Eighty extracted human molars were classified into four fluorosis groups according to the Thylstrup-Fejerskov Index (TFI) [TFI: 0, Healthy enamel; 1-3, mild; 4-5, moderate; 6-9, severe fluorosis]. All samples were analyzed by micro-Raman spectroscopy. The integral areas of ν(1) (960 cm(-1)) phosphate peak as well as B-type carbonate peak (1070 cm(-1)) were obtained to analyze structural differences among the specimens. Although the differences were not statistically significant (P > 0.05), the mean of integral areas of ν(1) phosphate peak among groups indicated greater mineralization in the severe fluorosis group. However, there were statistically significant differences in the intensities, and the integral areas of B-type carbonate peak among groups (P < 0.05). Therefore, mineralization of the carbonate peak at 1070 cm(-1) decreased significantly in fluorotic groups, suggesting that carbonate ions are easily dissolved in the presence of fluoride. Although structurally fluorotic teeth are not more susceptible to dental caries, serious alteration in its surface topography may cause retention of bacterial plaque and formation of enamel caries. Micro-Raman spectroscopy is a useful tool for analyzing the molecular structure of healthy and fluorotic human enamel.

Chemical vapor deposition synthesis of N-, P-, and Si-doped single-walled carbon nanotubes.

Here we report the synthesis of single-walled carbon nanotube bundles by chemical vapor deposition in the presence of electron donor elements (N, P, and Si). In order to introduce each dopant into the graphitic carbon lattice, different precursors containing the doping elements (benzylamine, pyrazine, triphenylphosphine, and methoxytrimethylsilane) were added at various concentrations into ethanol/ferrocene solutions. The synthesized nanotubes and byproduct were characterized by electron microscopy and Raman spectroscopy. Our results reveal intrinsic structural and electronic differences for the N-, P-, and Si- doped nanotubes. These tubes can now be tested for the fabrication of electronic nanodevices, and their performance can be observed.

Longitudinal cutting of pure and doped carbon nanotubes to form graphitic nanoribbons using metal clusters as nanoscalpels.

We report the use of transition metal nanoparticles (Ni or Co) to longitudinally cut open multiwalled carbon nanotubes in order to create graphitic nanoribbons. The process consists of catalytic hydrogenation of carbon, in which the metal particles cut sp(2) hybridized carbon atoms along nanotubes that results in the liberation of hydrocarbon species. Observations reveal the presence of unzipped nanotubes that were cut by the nanoparticles. We also report the presence of partially open carbon nanotubes, which have been predicted to have novel magnetoresistance properties.(1) The nanoribbons produced are typically 15-40 nm wide and 100-500 nm long. This method offers an alternative approach for making graphene nanoribbons, compared to the chemical methods reported recently in the literature.

Effects of 45-nm silver nanoparticles on coronary endothelial cells and isolated rat aortic rings.

This study was undertaken to determine whether silver nanoparticles (Ag-45 nm NPs) induce selective and specific biological effects, such as induction of proliferation and nitric oxide (NO) production, and cytotoxicity in coronary endothelial cells (CECs), and regulation of vascular tone in isolated rat aortic rings. Physical characterization of Ag-45 nm NPs by transmission electron microscopy (TEM) demonstrated that nanoparticles ranging in size from 10 to 90 nm had biological effects on CECs. Increasing concentrations of Ag-45 nm NPs exerted a dual effect on cell proliferation whereby proliferation was inhibited at low concentrations of NPs and stimulated at high concentrations. The effects of high, but not low, concentrations of Ag-45 nm NPs were dependent on NO because the effects were partially blocked by N(G)-nitro-L-arginine methyl ester (L-NAME). We have also shown that high, but not low, concentrations of Ag-45 nm NPs induce NO-dependent proliferation through activation of endothelial nitric oxide synthase (eNOS) by phosphorylation of Serine 1177. Moreover, the antiproliferative and proliferative effects of Ag-45 nm NPs were concentration-dependent and inversely correlated with cellular toxicity. In isolated rat aortic rings, a low concentration of NPs induced vasoconstriction and a high concentration stimulated vasodilation. The physiologic effects induced by a low concentration of Ag-45 nm NPs inhibited acetylcholine- (ACh-) induced NO-mediated relaxation. Vasodilation induced by a high concentration of NPs was partially abolished by L-NAME pretreatment. When the endothelium was removed from the rings, all physiologic responses were blocked. These results clearly demonstrate that the NPs have selective and specific effects on the vascular endothelium in a concentration-dependent manner and suggest that opposite effects could be associated with NPs of different sizes.

Spin polarized conductance in hybrid graphene nanoribbons using 5-7 defects.

We present a class of intramolecular graphene heterojunctions and use first-principles density functional calculations to describe their electronic, magnetic, and transport properties. The hybrid graphene and hybrid graphene nanoribbons have both armchair and zigzag features that are separated by an interface made up of pentagonal and heptagonal carbon rings. Contrary to conventional graphene sheets, the computed electronic density of states indicates that all hybrid graphene and nanoribbon systems are metallic. Hybrid nanoribbons are found to exhibit a remarkable width-dependent magnetic behavior and behave as spin polarized conductors.

Electron and phonon renormalization near charged defects in carbon nanotubes.

Owing to their influence on electrons and phonons, defects can significantly alter electrical conductance, and optical, mechanical and thermal properties of a material. Thus, understanding and control of defects, including dopants in low-dimensional systems, hold great promise for engineered materials and nanoscale devices. Here, we characterize experimentally the effects of a single defect on electrons and phonons in single-wall carbon nanotubes. The effects demonstrated here are unusual in that they are not caused by defect-induced symmetry breaking. Electrons and phonons are strongly coupled in sp(2) carbon systems, and a defect causes renormalization of electron and phonon energies. We find that near a negatively charged defect, the electron velocity is increased, which in turn influences lattice vibrations locally. Combining measurements on nanotube ensembles and on single nanotubes, we capture the relation between atomic response and the readily accessible macroscopic behaviour.

Bulk production of a new form of sp(2) carbon: crystalline graphene nanoribbons.

We report the use of chemical vapor deposition (CVD) for the bulk production (grams per day) of long, thin, and highly crystalline graphene ribbons (<20-30 microm in length) exhibiting widths of 20-300 nm and small thicknesses (2-40 layers). These layers usually exhibit perfect ABAB... stacking as in graphite crystals. The structure of the ribbons has been carefully characterized by several techniques and the electronic transport and gas adsorption properties have been measured. With this material available to researchers, it should be possible to develop new applications and physicochemical phenomena associated with layered graphene.

Magnetic behavior in zinc oxide zigzag nanoribbons.

We use first principles calculations to investigate the magnetic properties of zinc oxide nanoribbons with zigzag-terminated edges. The polarized spin density of states is calculated as a function of the nanoribbons width and thickness. All nanoribbons formed by a single layer exhibit a magnetic behavior independently of the width. By analyzing the charge density and spin density, we determine that the oxygen-dominated edge exhibits unpaired spins. When the thickness of the ribbons is increased, a magnetic moment is observed only for specific thicknesses.

Guiding electrical current in nanotube circuits using structural defects: a step forward in nanoelectronics.

Electrical current could be efficiently guided in 2D nanotube networks by introducing specific topological defects within the periodic framework. Using semiempirical transport calculations coupled with Landauer-Buttiker formalism of quantum transport in multiterminal nanoscale systems, we provide a detailed analysis of the processes governing the atomic-scale design of nanotube circuits. We found that when defects are introduced as patches in specific sites, they act as bouncing centers that reinject electrons along specific paths, via a wave reflection process. This type of defects can be incorporated while preserving the 3-fold connectivity of each carbon atom embedded within the graphitic lattice. Our findings open up a new way to explore bottom-up design, at the nanometer scale, of complex nanotube circuits which could be extended to 3D nanosystems and applied in the fabrication of nanoelectronic devices.

Soft purification of N-doped and undoped multi-wall carbon nanotubes.

A soft method for purifying multi-wall carbon nanotubes (N-doped and undoped) is presented. The technique includes a hydrothermal/ultrasonic treatment of the material in conjunction with other subsequent treatments, including the extraction of polyaromatic compounds, dissolution of metal particles, bundle exfoliation, and uniform dispersion. This method avoids harsh oxidation protocols that burn (via thermal treatments) or functionalize (by introducing chemical groups) the nanotubes. We show a careful analysis of each purification step and demonstrate that the technique is extremely efficient when characterizing the materials using scanning electron microscopy (SEM), energy dispersive x-ray analysis (EDAX), scanning tuneling electron microscopy (STEM), x-ray powder diffraction (XRD), diffuse reflectance Fourier transform infrared (DRFTIR) spectroscopy and thermogravimetric analysis (TGA).

Femtosecond laser nanosurgery of defects in carbon nanotubes.

All self-assembled nanostructures, like carbon nanotubes, exhibit structural imperfections that affect their electronic and mechanical properties and constitute a serious problem for the development of novel electronic nanodevices. Very common defects in nanotubes are pentagon-heptagon pairs, in which the replacement of four hexagons by two pentagons and two heptagons disrupts the perfect hexagonal lattice. In this work, we demonstrate that these defects can be eliminated efficiently with the help of femtosecond laser pulses. By performing nonadiabatic molecular dynamics simulations, we show that in the laser-induced electronic nonequilibrium the pentagon-heptagon pair is transformed back into four hexagons without producing any irreversible damage to the rest of the nanotube.

Shape and complexity at the atomic scale: the case of layered nanomaterials.

In nature there are numerous layered compounds, some of which could be curved so as to form fascinating nanoshapes with novel properties. Graphite is at present the main example of a very flexible layered structure, which is able to form cylinders (nanotubes) and cages (fullerenes), but there are others. While fullerenes possess positive curvature due to pentagonal rings of carbon, there are other structures which could include heptagonal or higher membered rings. In fact, fullerenes and nanotubes could display negative curvature, thus forming nanomaterials possessing unexpected electronic and mechanical properties. The effect of curvature in other nano-architectures, such as in boron nitride and metal dichalcogenides, is also discussed in this account. Electron irradiation is a tool able to increase the structural complexity of layered materials. In this context, we describe the coalescence of carbon nanotubes and C(60) molecules. The latter results now open up an alternative approach to producing and manipulating novel nanomaterials in the twenty-first century.

The carbon nanocosmos: novel materials for the twenty-first century.

Carbon is one of the elements most abundant in nature. It is essential for living organisms and, as an element, occurs in several morphologies. Nowadays, carbon is encountered widely in our daily lives in its various forms and compounds, such as graphite, diamond, hydrocarbons, fibres, soot, oil, complex molecules, etc. However, in the last decade, carbon science and technology have enlarged its scope following the discovery of fullerenes (carbon nanocages) and the identification of carbon nanotubes (rolled graphene sheets). These novel nanostructures possess physico-chemical properties different from those of bulk graphite and diamond. It is expected that numerous technological applications will arise using such fascinating structures. This account summarizes the most relevant achievements regarding the production, properties and applications of nanoscale carbon structures and, in particular, of carbon nanotubes. It is believed that nanocarbons will be crucial for the development of emerging technologies in the following years.