James M. Tour

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.

Growth of graphene from solid carbon sources

Monolayer graphene was first obtained as a transferable material in 2004 and has stimulated intense activity among physicists, chemists and material scientists. Much research has been focused on developing routes for obtaining large sheets of monolayer or bilayer graphene. This has been recently achieved by chemical vapour deposition (CVD) of CH4 or C2H2 gases on copper or nickel substrates. But CVD is limited to the use of gaseous raw materials, making it difficult to apply the technology to a wider variety of potential feedstocks. Here we demonstrate that large area, high-quality graphene with controllable thickness can be grown from different solid carbon sources—such as polymer films or small molecules—deposited on a metal catalyst substrate at temperatures as low as 800 °C. Both pristine graphene and doped graphene were grown with this one-step process using the same experimental set-up.

Are single molecular wires conducting

Molecular wire candidates inserted into “nonconducting” n-dodecanethiol self-assembled monolayers on Au{111} were probed by scanning tunneling microscopy (STM) and microwave frequency alternating current STM at high tunnel junction impedance (100 gigohms) to assess their electrical properties. The inserted conjugated molecules, which were 4,4′-di(phenylene-ethynylene)benzenethiolate derivatives, formed single molecular wires that extended from the Au{111} substrate to about 7 angstroms above and had very high conductivity as compared with that of the alkanethiolate.

Diazonium Functionalization of Surfactant-Wrapped Chemically Converted Graphene Sheets

Surfactant-wrapped chemically converted graphene sheets obtained from reduction of graphene oxide with hydrazine were functionalized by treatment with aryl diazonium salts. The nanosheets are characterized by X-ray photoelectron spectroscopy, attenuated total reflectance infrared spectroscopy, Raman spectroscopy, atomic force microscopy, and transmission electron microscopy. The resulting functionalized nanosheets disperse readily in polar aprotic solvents, allowing alternative avenues for simple incorporation into different polymer matrices.

Covalent chemistry of single-wall carbon nanotubes

Despite the extraordinary promise of single-wall carbon nanotubes, their realistic application in materials and devices has been hindered by processing and manipulation difficulties. Now that this unique material is readily available in near kilogram quantities (albeit still at high cost), research into means of chemical alteration is in full swing. The covalent attachment of appropriate moieties is anticipated to facilitate applications development by improving solubility and ease of dispersion, and providing for chemical attachment to surfaces and polymer matrices. While it is clear that more investigation is needed to elucidate the nature and locality of covalently attached moieties, developments to date indicate that carbon nanotubes may indeed be considered a true segment of organic chemistry. In this contribution, we review the current state of carbon nanotube covalent chemistry, and convey our anxious expectation that further developments will follow.

Materials Science: Nanotube composites

A carbon revolution has occurred — carbon atoms can be coaxed into several topologies to make materials with unique properties. Nanotubes are the vanguard of this innovation, and are on the cusp of commercial exploitation as the multifunctional components of the next generation of composite materials.

Mesoporous silicon particles as a multistage delivery system for imaging and therapeutic applications.

Many nanosized particulate systems are being developed as intravascular carriers to increase the levels of therapeutic agents delivered to targets, with the fewest side effects. The surface of these carriers is often functionalized with biological recognition molecules for specific, targeted delivery. However, there are a series of biological barriers in the body that prevent these carriers from localizing at their targets at sufficiently high therapeutic concentrations. Here we show a multistage delivery system that can carry, release over time and deliver two types of nanoparticles into primary endothelial cells. The multistage delivery system is based on biodegradable and biocompatible mesoporous silicon particles that have well-controlled shapes, sizes and pores. The use of this system is envisioned to open new avenues for avoiding biological barriers and delivering more than one therapeutic agent to the target at a time, in a time-controlled fashion.

Molecular random access memory cell

Electronically programmable memory devices utilizing molecular self-assembled monolayers are reported. The devices exhibit electronically programmable and erasable memory bits compatible with conventional threshold levels and a memory cell applicable to a random access memory is demonstrated. Bit retention times >15 min have been observed.

Nanoscale metal/self-assembled monolayer/metal heterostructures

We present the investigation of novel metal/organic monolayer/metal heterostructure diodes. Our technique provides well-defined, stable, and reproducible metallic contacts to a self-assembled monolayer of 4-thioacetylbiphenyl with nanoscale area. Electronic transport measurements show a prominent rectifying behavior arising from the asymmetry of the molecular heterostructure. Variable-temperature measurements reveal that thermal emission of electrons over a barrier of 0.22 eV dominates for electron injection from Ti into the organic layer while the transport for electron injection from Au into the organic layer satisfies the formula for hopping conduction.

Large-Scale Growth and Characterizations of Nitrogen-Doped Monolayer Graphene Sheets

In-plane heteroatom substitution of graphene is a promising strategy to modify its properties. Doping with electron-donor nitrogen heteroatoms can modulate the electronic properties of graphene to produce an n-type semiconductor. Here we demonstrate the growth of monolayer nitrogen-doped graphene in centimeter-scale sheets using a chemical vapor deposition process with pyridine as the sole source of both carbon and nitrogen. High-resolution transmission microscopy and Raman mapping characterizations indicate that the nitrogen-doped graphene sheets are uniformly monolayered. The existence of nitrogen-atom substitution in the graphene planes was confirmed by X-ray photoelectron spectroscopy. Electrical measurements show that the nitrogen-doped graphene exhibits an n-type behavior, different from pristine graphene. The preparation of large-area nitrogen-doped graphene provides a viable route to modify the properties of monolayer graphene and promote its applications in electronic devices.