Alexander Sinitskii

Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons

Graphene, or single-layered graphite, with its high crystallinity and interesting semimetal electronic properties, has emerged as an exciting two-dimensional material showing great promise for the fabrication of nanoscale devices. Thin, elongated strips of graphene that possess straight edges, termed graphene ribbons, gradually transform from semiconductors to semimetals as their width increases, and represent a particularly versatile variety of graphene. Several lithographic, chemical and synthetic procedures are known to produce microscopic samples of graphene nanoribbons, and one chemical vapour deposition process has successfully produced macroscopic quantities of nanoribbons at 950 °C. Here we describe a simple solution-based oxidative process for producing a nearly 100% yield of nanoribbon structures by lengthwise cutting and unravelling of multiwalled carbon nanotube (MWCNT) side walls. Although oxidative shortening of MWCNTs has previously been achieved, lengthwise cutting is hitherto unreported. Ribbon structures with high water solubility are obtained. Subsequent chemical reduction of the nanoribbons from MWCNTs results in restoration of electrical conductivity. These early results affording nanoribbons could eventually lead to applications in fields of electronics and composite materials where bulk quantities of nanoribbons are required.

Spontaneous high-concentration dispersions and liquid crystals of graphene

Graphene combines unique electronic properties and surprising quantum effects with outstanding thermal and mechanical properties. Many potential applications, including electronics and nanocomposites, require that graphene be dispersed and processed in a fluid phase. Here, we show that graphite spontaneously exfoliates into single-layer graphene in chlorosulphonic acid, and dissolves at isotropic concentrations as high as approximately 2 mg ml(-1), which is an order of magnitude higher than previously reported values. This occurs without the need for covalent functionalization, surfactant stabilization, or sonication, which can compromise the properties of graphene or reduce flake size. We also report spontaneous formation of liquid-crystalline phases at high concentrations ( approximately 20-30 mg ml(-1)). Transparent, conducting films are produced from these dispersions at 1,000 Omega square(-1) and approximately 80% transparency. High-concentration solutions, both isotropic and liquid crystalline, could be particularly useful for making flexible electronics as well as multifunctional fibres.

Lower-Defect Graphene Oxide Nanoribbons from Multiwalled Carbon Nanotubes

An improved method is described for the production of graphene oxide nanoribbons (GONRs) via longitudinal unzipping of multiwalled carbon nanotubes. The method produces GONRs with fewer defects and/or holes on the basal plane, maintains narrow ribbons <100 nm wide, and maximizes the high aspect ratio. Changes in the reaction conditions such as acid content, time, and temperature were investigated. The new, optimized method which introduces a second, weaker acid into the system, improves the selectivity of the oxidative unzipping presumably by in situ protection of the vicinal diols formed on the basal plane of graphene during the oxidation, and thereby prevents their overoxidation and subsequent hole generation. The optimized GONRs exhibit increased electrical conductivity over those chemically reduced nanoribbons produced by previously reported procedures.

Kinetics of Diazonium Functionalization of Chemically Converted Graphene Nanoribbons

We demonstrate that graphene nanoribbons (GNRs) produced by the oxidative unzipping of carbon nanotubes can be chemically functionalized by diazonium salts. We show that functional groups form a thin layer on a GNR and modify its electrical properties. The kinetics of the functionalization can be monitored by probing the electrical properties of GNRs, either in vacuum after the grafting, or in situ in the solution. We derive a simple kinetics model that describes the change in the electrical properties of GNRs. The reaction of GNRs with 4-nitrobenzene diazonium tetrafluoroborate is reasonably fast, such that >60% of the maximum change in the electrical properties is observed after less than 5 min of grafting at room temperature.

Layer-by-Layer Removal of Graphene for Device Patterning

Reactions of graphene with zinc enable etching of a single graphene layer. The patterning of graphene is useful in fabricating electronic devices, but existing methods do not allow control of the number of layers of graphene that are removed. We show that sputter-coating graphene and graphene-like materials with zinc and dissolving the latter with dilute acid removes one graphene layer and leaves the lower layers intact. The method works with the four different types of graphene and graphene-like materials: graphene oxide, chemically converted graphene, chemical vapor–deposited graphene, and micromechanically cleaved (“clear-tape”) graphene. On the basis of our data, the top graphene layer is damaged by the sputtering process, and the acid treatment removes the damaged layer of carbon. When used with predesigned zinc patterns, this method can be viewed as lithography that etches the sample with single-atomic-layer resolution.

Highly conductive graphene nanoribbons by longitudinal splitting of carbon nanotubes using potassium vapor.

Here we demonstrate that graphene nanoribbons (GNRs) free of oxidized surfaces can be prepared in large batches and 100% yield by splitting multiwalled carbon nanotubes (MWCNTs) with potassium vapor. If desired, exfoliation is attainable in a subsequent step using chlorosulfonic acid. The low-defect density of these GNRs is indicated by their electrical conductivity, comparable to that of graphene derived from mechanically exfoliated graphite. The possible origins of directionally selective splitting of MWCNTs have been explored using computer modeling, and plausible explanations for the unique role of potassium were found.

Patterning Graphene through the Self-Assembled Templates: Toward Periodic Two-Dimensional Graphene Nanostructures with Semiconductor Properties

Periodic graphene nanostructures are fabricated via patterning graphene through the self-assembled monolayers of monodisperse colloidal microspheres. The resulting structures exhibit promising electronic properties featuring high conductivities and ON-OFF ratios up to 10. The apparent advantages of the presented method are the possibilities of fabricating periodic graphene nanostructures with different periodicities, ranging from ∼100 nm to several μm, and also varying the periodicity and the neck width independently. The use of the presented method yields graphene nanostructures with variable electronic properties.

Highly selective gas sensor arrays based on thermally reduced graphene oxide

The electrical properties of reduced graphene oxide (rGO) have been previously shown to be very sensitive to surface adsorbates, thus making rGO a very promising platform for highly sensitive gas sensors. However, poor selectivity of rGO-based gas sensors remains a major problem for their practical use. In this paper, we address the selectivity problem by employing an array of rGO-based integrated sensors instead of focusing on the performance of a single sensing element. Each rGO-based device in such an array has a unique sensor response due to the irregular structure of rGO films at different levels of organization, ranging from nanoscale to macroscale. The resulting rGO-based gas sensing system could reliably recognize analytes of nearly the same chemical nature. In our experiments rGO-based sensor arrays demonstrated a high selectivity that was sufficient to discriminate between different alcohols, such as methanol, ethanol and isopropanol, at a 100% success rate. We also discuss a possible sensing mechanism that provides the basis for analyte differentiation.

Electronic two-terminal bistable graphitic memories

Transistors are the basis for electronic switching and memory devices as they exhibit extreme reliabilities with on/off ratios of 10(4)-10(5), and billions of these three-terminal devices can be fabricated on single planar substrates. On the other hand, two-terminal devices coupled with a nonlinear current-voltage response can be considered as alternatives provided they have large and reliable on/off ratios and that they can be fabricated on a large scale using conventional or easily accessible methods. Here, we report that two-terminal devices consisting of discontinuous 5-10 nm thin films of graphitic sheets grown by chemical vapour deposition on either nanowires or atop planar silicon oxide exhibit enormous and sharp room-temperature bistable current-voltage behaviour possessing stable, rewritable, non-volatile and non-destructive read memories with on/off ratios of up to 10(7) and switching times of up to 1 micros (tested limit). A nanoelectromechanical mechanism is proposed for the unusually pronounced switching behaviour in the devices.

Longitudinal Splitting of Boron Nitride Nanotubes for the Facile Synthesis of High Quality Boron Nitride Nanoribbons

Boron nitride nanoribbons (BNNRs), the boron nitride structural equivalent of graphene nanoribbons (GNRs), are predicted to possess unique electronic and magnetic properties. We report the synthesis of BNNRs through the potassium-intercalation-induced longitudinal splitting of boron nitride nanotubes (BNNTs). This facile, scalable synthesis results in narrow (down to 20 nm), few sheet (typically 2-10), high crystallinity BNNRs with very uniform widths. The BNNRs are at least 1 μm in length with minimal defects within the ribbon plane and along the ribbon edges.