Humberto Terrones

Bulk Production of a New Form of sp2 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.

Enhanced magnetic coercivities in Fe nanowires

We describe a way of generating films (<2 mm2; <40 μm thick) of aligned Fe-filled carbon nanotubes. These Fe nanowires are usually composed of single Fe crystals, and have dimensions from 5–40 nm outer diameter and <10 μm in length. The carbon tubes, which coat the wires, have external diameters of ∼20–70 nm and are <40 μm in length. High-resolution electron energy loss spectroscopy, x-ray powder diffraction, and elemental mapping of the tubular structures reveal only characteristic metallic signals and the effective absence of oxygen (or any other nonmetallic element) within the wires. The material exhibits coercivities in the 430–1070 Oe range, i.e., greater than those reported for Ni and Co nanowires.

Efficient route to large arrays of CNx nanofibers by pyrolysis of ferrocene/melamine mixtures

We report a high-yield route to two-dimensional arrays (<400×400 μm2) of aligned C49Nx (x ⩽ 1) nanofibers (<100 nm o.d.; <60 μm length), by pyrolyzing mixtures of ferrocene and melamine at 950–1050 °C under an Ar flow. The fibers exhibit unusual interlinked stacked-cone morphologies, ascribed to the presence of nitrogen. High-resolution electron energy-loss spectroscopy of the individual fibers reveals a 2% nitrogen content with ionization energies mainly at ∼400.9 eV, corresponding to N bonded to three C atoms within a hexagonal framework. The nanofibers may be useful for the economic fabrication of field emission sources and robust composites.

Nitrogen-mediated carbon nanotube growth: diameter reduction, metallicity, bundle dispersability, and bamboo-like structure formation.

Carbon nanotube growth in the presence of nitrogen has been the subject of much experimental scrutiny, sparking intense debate about the role of nitrogen in the formation of diverse structural features, including shortened length, reduced diameters, and bamboo-like multilayered nanotubules. In this paper, the origin of these features is elucidated using a combination of experimental and theoretical techniques, showing that N acts as a surfactant during growth. N doping enhances the formation of smaller diameter tubes. It can also promote tube closure which includes a relatively large amount of N atoms into the tube lattice, leading to bamboo-like structures. Our findings demonstrate that the mechanism is independent of the tube chirality and suggest a simple procedure for controlling the growth of bamboo-like nanotube morphologies.

Heterodoped nanotubes: theory, synthesis, and characterization of phosphorus-nitrogen doped multiwalled carbon nanotubes.

Arrays of multiwalled carbon nanotubes doped with phosphorus (P) and nitrogen (N) are synthesized using a solution of ferrocene, triphenyl-phosphine, and benzylamine in conjunction with spray pyrolysis. We demonstrate that iron phosphide (Fe(3)P) nanoparticles act as catalysts during nanotube growth, leading to the formation of novel PN-doped multiwalled carbon nanotubes. The samples were examined by high resolution electron microscopy and microanalysis techniques, and their chemical stability was explored by means of thermogravimetric analysis in the presence of oxygen. The PN-doped structures reveal important morphology and chemical changes when compared to N-doped nanotubes. These types of heterodoped nanotubes are predicted to offer many new opportunities in the fabrication of fast-response chemical sensors.

Aligned CNx nanotubes by pyrolysis of ferrocene/C60 under NH3 atmosphere

Aligned CNx (x<0.1) nanotubes have been generated by pyrolyzing ferrocene/C60 mixtures at 1050 °C in an ammonia atmosphere. The structure and composition of the product were determined by high-resolution transmission electron microscopy and high spatial resolution electron energy-loss spectroscopy. The CNx tubes (15–70 nm diameter, <50 μm length) grown in large flakes (<3 mm2) consist of a reduced number of “graphitic” layers (<15 on either side) arranged in a bamboo-like structure. Areas of high nitrogen concentration were found within curved or corrugated “graphite-like” domains. The observation of a well-developed double peak in the σ* feature of the N K-edge suggests that the material has not undergone the transition to the fullerene-like phase known for nitrogenated carbons. Incorporation of nitrogen from the gas phase (NH3) into CNx nanotubes therefore leads to improved and more efficient N substitution into the network as compared to the synthesis with solid nitrogen-containing precursors reported ...

Heterojunctions between metals and carbon nanotubes as ultimate nanocontacts

We report the controlled formation and characterization of heterojunctions between carbon nanotubes and different metal nanocrystals (Fe, Co, Ni, and FeCo). The heterojunctions are formed from metal-filled multiwall carbon nanotubes (MWNTs) via intense electron beam irradiation at temperatures in the range of 450–700 °C and observed in situ in a transmission electron microscope. Under irradiation, the segregation of metal and carbon atoms occurs, leading to the formation of heterojunctions between metal and graphite. Metallic conductivity of the metal–nanotube junctions was found by using in situ transport measurements in an electron microscope. Density functional calculations show that these structures are mechanically strong, the bonding at the interface is covalent, and the electronic states at and around the Fermi level are delocalized across the entire system. These properties are essential for the application of such heterojunctions as contacts in electronic devices and vital for the fabrication of robust nanotube–metal composite materials.

Boron Nitride Nanoribbons Become Metallic

Standard spin-polarized density functional theory calculations have been conducted to study the electronic structures and magnetic properties of O and S functionalized zigzag boron nitride nanoribbons (zBNNRs). Unlike the semiconducting and nonmagnetic H edge-terminated zBNNRs, the O edge-terminated zBNNRs have two energetically degenerate magnetic ground states with a ferrimagnetic character on the B edge, both of which are metallic. In contrast, the S edge-terminated zBNNRs are nonmagnetic albeit still metallic. An intriguing coexistence of two different Peierls-like distortions is observed for S edge-termination that manifests as a strong S dimerization at the B zigzag edge and a weak S trimerization at the N zigzag edge, dictated by the band fillings at the vicinity of the Fermi level. Nevertheless, metallicity is retained along the S wire on the N edge due to the partial filling of the band derived from the p(z) orbital of S. A second type of functionalization with O or S atoms embedded in the center of zBNNRs yields semiconducting features. Detailed examination of both types of functionalized zBNNRs reveals that the p orbitals on O or S play a crucial role in mediating the electronic structures of the ribbons. We suggest that O and S functionalization of zBNNRs may open new routes toward practical electronic devices based on boron nitride materials.

Comparison study of semi-crystalline and highly crystalline multiwalled carbon nanotubes

Very different types of straight and long multiwalled carbon nanotubes, ranging from semi-crystalline to highly crystalline, are obtained using a floating reactant method, by merely changing the flow rate of the carrier gas. Graphitization behaviors of these nanotubes are studied comparatively in terms of their microstructure and morphology, showing a large change in structure for the semi-crystalline nanotubes, but little change in the highly crystalline nanotubes with heat treatment.

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.