<Emphasis Type="Italic">In situ</Emphasis> imaging of layer-by-layer sublimation of suspended graphene

An individual suspended graphene sheet was connected to a scanning tunneling microscopy probe inside a transmission electron microscope, and Joule heated to high temperatures. At high temperatures and under electron beam irradiation, the few-layer graphene sheets were removed layer-by-layer in the viewing area until a monolayer graphene was formed. The layer-by-layer peeling was initiated at vacancies in individual graphene layers. The vacancies expanded to form nanometer-sized holes, which then grew along the perimeter and propagated to both the top and bottom layers of a bilayer graphene joined by a bilayer edge. The layer-by-layer peeling was induced by atom sublimation caused by Joule heating and facilitated by atom displacement caused by high-energy electron irradiation, and may be harnessed to control the layer thickness of graphene for device applications.      

Configuration-sensitive molecular sensing on doped graphene sheets

We show by molecular dynamics simulations that configuration-sensitive molecular spectroscopy can be realized on optimally doped graphene sheets vibrated by an oscillatory electric field. High selectivity of the spectroscopy is achieved by maximizing Coulombic binding between the detected molecule and a specific nest, formed for this molecule on the graphene sheet by substituting selected carbon atoms with boron and nitrogen dopants. One can detect binding of different isomers to the nest from the frequency shifts of selected vibrational modes of the combined system. As an illustrative example, we simulate detection of hexanitrostilbene enantiomers in chiral nests formed on graphene.      

Graphene-like bilayer hexagonal silicon polymorph

We present molecular dynamics simulation evidence for a freezing transition from liquid silicon to quasi-two-dimensional (quasi-2D) bilayer silicon in a slit nanopore. This new quasi-2D polymorph of silicon exhibits a bilayer hexagonal structure in which the covalent coordination number of every silicon atom is four. Quantum molecular dynamics simulations show that the stand-alone bilayer silicon (without the confinement) is still stable at 400 K. Electronic band-structure calculations suggest that the bilayer hexagonal silicon is a quasi-2D semimetal, similar to a graphene monolayer, but with an indirect zero band gap.      

Mechanical properties of freely suspended atomically thin dielectric layers of mica

We have studied the elastic deformation of freely suspended atomically thin sheets of muscovite mica, a widely used electrical insulator in its bulk form. Using an atomic force microscope, we carried out bending test experiments to determine the Young’s modulus and the initial pre-tension of mica nanosheets with thicknesses ranging from 14 layers down to just one bilayer. We found that their Young’s modulus is high (190 GPa), in agreement with the bulk value, which indicates that the exfoliation procedure employed to fabricate these nanolayers does not introduce a noticeable amount of defects. Additionally, ultrathin mica shows low pre-strain and can withstand reversible deformations up to tens of nanometers without breaking. The low pre-tension and high Young’s modulus and breaking force found in these ultrathin mica layers demonstrates their prospective use as a complement for graphene in applications requiring flexible insulating materials or as reinforcement in nanocomposites.      

Facile synthesis and application of Ag-chemically converted graphene nanocomposite

An in situ chemical synthesis approach has been employed to prepare an Ag-chemically converted graphene (CCG) nanocomposite. The reduction of graphene oxide sheets was accompanied by generation of Ag nanoparticles. The structure and composition of the nanocomposites were confirmed by means of transmission electron microscopy (TEM), atomic force microscopy (AFM) and X-ray diffraction. TEM and AFM results suggest a homogeneous distribution of Ag nanoparticles (5–10 nm in size) on CCG sheets. The intensities of the Raman signals of CCG in such nanocomposites are greatly increased by the attached silver nanoparticles, i.e., there is surface-enhanced Raman scattering activity. In addition, it was found that the antibacterial activity of free Ag nanoparticles is retained in the nanocomposites, which suggests they can be used as graphene-based biomaterials.      

Shedding light on the crystallographic etching of multi-layer graphene at the atomic scale

The controlled etching of graphite and graphene by catalytic hydrogenation is potentially a key engineering route for the fabrication of graphene nanoribbons with atomic precision. The hydrogenation mechanism, though, remains poorly understood. In this study we exploit the benefits of aberration-corrected high-resolution transmission electron microscopy to gain insight to the hydrogenation reaction. The etch tracks are found to be commensurate with the graphite lattice. Catalyst particles at the head of an etch channel are shown to be faceted and the angles between facets are multiples of 30°. Thus, the angles between facets are also commensurate with the graphite lattice. In addition, the results of a post-annealing step suggest that all catalyst particles—even if they are not involved in etching—are actively forming methane during the hydrogenation reaction. Furthermore, the data point against carbon dissolution being a key mechanism during the hydrogenation process.      

Efficient synthesis of graphene nanoribbons sonochemically cut from graphene sheets

We report a facile approach to synthesize narrow and long graphene nanoribbons (GNRs) by sonochemically cutting chemically derived graphene sheets (GSs). The yield of GNRs can reach ∼5 wt% of the starting GSs. The resulting GNRs are several micrometers in length, with ∼75% being single-layer, and ∼40% being narrower than 20 nm in width. A chemical tailoring mechanism involving oxygen-unzipping of GSs under sonochemical conditions is proposed on the basis of experimental observations and previously reported theoretical calculations; it is suggested that the formation and distribution of line faults on graphite oxide and GSs play crucial roles in the formation of GNRs. These results open up the possibilities of the large-scale synthesis and various technological applications of GNRs.      

Synthesis and Ex situ doping of ZnTe and ZnSe nanostructures with extreme aspect ratios

We report synthesis windows for growth of millimeter-long ZnTe nanoribbons and ZnSe nanowires using vapor transport. By tuning the local conditions at the growth substrate, high aspect ratio nanostructures can be synthesized. A Cu-ion immersion doping method was applied, producing strongly p-type conduction in ZnTe and ionic conduction in ZnSe. These extreme aspect ratio wide-bandgap semiconductors have great potential for high density nanostructured optoelectronic circuits.      

Ionic liquid-assisted one-step hydrothermal synthesis of TiO2-reduced graphene oxide composites

We have demonstrated a facile and efficient strategy for the fabrication of soluble reduced graphene oxide sheets (RGO) and the preparation of titanium oxide (TiO₂) nanoparticle-RGO composites using a modified one-step hydrothermal method. It was found that graphene oxide could be easily reduced under solvothermal conditions with ascorbic acid as reductant, with concomitant growth of TiO₂ particles on the RGO surface. The TiO₂-RGO composite has been thoroughly characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and thermogravimetric analysis. Microscopy techniques (scanning electron microscopy, atomic force microscopy, and transmission electron microscopy) have been employed to probe the morphological characteristics as well as to investigate the exfoliation of RGO sheets. The TiO₂-RGO composite exhibited excellent photocatalysis of hydrogen evolution.      

Role of catalysts in the surface synthesis of single-walled carbon nanotubes

We demonstrate the role of catalysts in the surface growth of single-walled carbon nanotubes (SWNTs) by reviewing recent progress in the surface synthesis of SWNTs. Three effects of catalysts on surface synthesis are studied: type of catalyst, the relationship between the size of catalyst particles and carbon feeding rates, and interactions between catalysts and substrates. Understanding of the role of catalysts will contribute to our ability to control the synthesis of SWNTs on various substrates and facilitate the fabrication of nanotube-based devices.      

Nanopumping molecules via a carbon nanotube

We demonstrate the feasibility of using a carbon nanotube to nanopump molecules. Molecular dynamics simulations show that the transport and ejection of a C₂₀ molecule via a single-walled carbon nanotube (SWNT) can be achieved by a sustained mechanical actuation driven by two oscillating tips. The optimal condition for nanopumping is found when the tip oscillation frequency and magnitude correlate to form quasi steady-state mechanical wave propagation in the SWNT, so that the energy transfer process is optimal leading to maximal molecular translational motion and minimal rotational motion. Our finding provides a potentially useful mechanism for using an SWNT as a vehicle to deliver large drug molecules.      

An essay on synthetic chemistry of colloidal nanocrystals

The central goal of synthetic chemistry of colloidal nanocrystals at present is to discover functional materials. Such functional materials should help mankind to meet the tough challenges brought by the rapid depletion of natural resources and the significant increase of population with higher and higher living standards. With this thought in mind, this essay discusses the basic guidelines for developing this new branch of synthetic chemistry, including rational synthetic strategies, functional performance, and green chemistry principles.      

Synthesis of high magnetic moment CoFe nanoparticles via interfacial diffusion in core/shell structured Co/Fe nanoparticles

We report the synthesis of high magnetic moment CoFe nanoparticles via the diffusion of Co and Fe in core/shell structured Co/Fe nanoparticles. In an organic solution, Co nanoparticles were coated with a layer of Fe to form a Co/Fe core/shell structure. Further raising the solution temperature led to inter-diffusion of Co and Fe and formation of CoFe alloy nanoparticles. These nanoparticles have high saturation magnetization of up to 192 emu/g CoFe and can be further stabilized by thermal annealing at 600 °C. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. These two authors made an equal contribution to the work.     

Facile, noncovalent decoration of graphene oxide sheets with nanocrystals

Facile dry decoration of graphene oxide sheets with aerosol Ag nanocrystals synthesized from an arc plasma source has been demonstrated using an electrostatic force directed assembly technique at room temperature. The Ag nanocrystal-graphene oxide hybrid structure was characterized by transmission electron microscopy (TEM) and selected area diffraction. The ripening of Ag nanocrystals on a graphene oxide sheet was studied by consecutive TEM imaging of the same region on a sample after heating in Ar at elevated temperatures of 100 °C, 200 °C, and 300 °C. The average size of Ag nanocrystals increased and the number density decreased after the annealing process. In particular, migration and coalescence of Ag nanocrystals were observed at a temperature as low as 100 °C, suggesting a van der Waals interaction between the Ag nanocrystal and the graphene oxide sheet. The availability of affordable graphene-nanocrystal structures and their fundamental properties will open up new opportunities for nanoscience and nanotechnology and accelerate their applications. This article is published with open access at Springerlink.com     

Thermoelectric properties of p-type PbSe nanowires

The thermoelectric properties of individual solution-phase synthesized p-type PbSe nanowires have been examined. The nanowires showed near degenerately doped charge carrier concentrations. Compared to the bulk, the PbSe nanowires exhibited a similar Seebeck coefficient and a significant reduction in thermal conductivity in the temperature range 20 K to 300 K. Thermal annealing of the PbSe nanowires allowed their thermoelectric properties to be controllably tuned by increasing their carrier concentration or hole mobility. After optimal annealing, single PbSe nanowires exhibited a thermoelectric figure of merit (ZT) of 0.12 at room temperature.      

Bending-induced conductance increase in individual semiconductor nanowires and nanobelts

Reliable ohmic contacts were established in order to study the strain sensitivity of nanowires and nanobelts. Significant conductance increases of up to 113% were observed on bending individual ZnO nanowires or CdS nanobelts. This bending strain-induced conductance enhancement was confirmed by a variety of bending measurements, such as using different manipulating tips (silicon, glass or tungsten) to bend the nanowires or nanobelts, and is explained by bending-induced effective tensile strain based on the principle of the piezoresistance effect. This article is published with open access at Springerlink.com     

Is graphene aromatic?

We analyze the chemical bonding in graphene using a fragmental approach, the adaptive natural density partitioning method, electron sharing indices, and nucleus-independent chemical shift indices. We prove that graphene is aromatic, but its aromaticity is different from the aromaticity in benzene, coronene, or circumcoronene. Aromaticity in graphene is local with two π-electrons delocalized over every hexagon ring. We believe that the chemical bonding picture developed for graphene will be helpful for understanding chemical bonding in defects such as point defects, single-, double-, and multiple vacancies, carbon adatoms, foreign adatoms, substitutional impurities, and new materials that are derivatives of graphene.      

Raman spectroscopy and imaging of graphene

Graphene has many unique properties that make it an ideal material for fundamental studies as well as for potential applications. Here we review recent results on the Raman spectroscopy and imaging of graphene. We show that Raman spectroscopy and imaging can be used as a quick and unambiguous method to determine the number of graphene layers. The strong Raman signal of single layer graphene compared to graphite is explained by an interference enhancement model. We have also studied the effect of substrates, the top layer deposition, the annealing process, as well as folding (stacking order) on the physical and electronic properties of graphene. Finally, Raman spectroscopy of epitaxial graphene grown on a SiC substrate is presented and strong compressive strain on epitaxial graphene is observed. The results presented here are highly relevant to the application of graphene in nano-electronic devices and help in developing a better understanding of the physical and electronic properties of graphene. This article is published with open access at Springerlink.com     

Recovery of edge states of graphene nanoislands on an iridium substrate by silicon intercalation

Finite-sized graphene sheets, such as graphene nanoislands (GNIs), are promising candidates for practical applications in graphene-based nanoelectronics. GNIs with well-defined zigzag edges are predicted to have spin-polarized edge-states similar to those of zigzag-edged graphene nanoribbons, which can achieve graphene spintronics. However, it has been reported that GNIs on metal substrates have no edge states because of interactions with the substrate.We used a combination of scanning tunneling microscopy, spectroscopy, and density functional theory calculations to demonstrate that the edge states of GNIs on an Ir substrate can be recovered by intercalating a layer of Si atoms between the GNIs and the substrate. We also found that the edge states gradually shift to the Fermi level with increasing island size. This work provides a method to investigate spin-polarized edge states in high-quality graphene nanostructures on a metal substrate.

Open image in new window

     

Growth of large-area single- and Bi-layer graphene by controlled carbon precipitation on polycrystalline Ni surfaces

We report graphene films composed mostly of one or two layers of graphene grown by controlled carbon precipitation on the surface of polycrystalline Ni thin films during atmospheric chemical vapor deposition (CVD). Controlling both the methane concentration during CVD and the substrate cooling rate during graphene growth can significantly improve the thickness uniformity. As a result, one- or two- layer graphene regions occupy up to 87% of the film area. Single layer coverage accounts for 5%–11% of the overall film. These regions expand across multiple grain boundaries of the underlying polycrystalline Ni film. The number density of sites with multilayer graphene/graphite (>2 layers) is reduced as the cooling rate decreases. These films can also be transferred to other substrates and their sizes are only limited by the sizes of the Ni film and the CVD chamber. Here, we demonstrate the formation of films as large as 1 in². These findings represent an important step towards the fabrication of large-scale high-quality graphene samples. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users.