Nucleation of single-walled carbon nanotubes

The nucleation pathway for single-wall carbon nanotubes on a metal surface is demonstrated by a series of total energy calculations using density functional theory. Incorporation of pentagons at an early stage of nucleation is energetically favorable as they reduce the number of dangling bonds and facilitate curvature of the structure and bonding to the metal. In the presence of the metal surface, nucleation of a closed cap or a capped single-wall carbon nanotube is overwhelmingly favored compared to any structure with dangling bonds or to a fullerene.     

Revealing the Preferred Interlayer Orientations and Stackings of Two‐Dimensional Bilayer Gallium Selenide Crystals

Characterizing and controlling the interlayer orientations and stacking orders of two‐dimensional (2D) bilayer crystals and van der Waals (vdW) heterostructures is crucial to optimize their electrical and optoelectronic properties. The four polymorphs of layered gallium selenide (GaSe) crystals that result from different layer stackings provide an ideal platform to study the stacking configurations in 2D bilayer crystals. Through a controllable vapor‐phase deposition method, bilayer GaSe crystals were selectively grown and their two preferred 0° or 60° interlayer rotations were investigated. The commensurate stacking configurations (AA′ and AB stacking) in as‐grown bilayer GaSe crystals are clearly observed at the atomic scale, and the Ga‐terminated edge structure was identified using scanning transmission electron microscopy. Theoretical analysis reveals that the energies of the interlayer coupling are responsible for the preferred orientations among the bilayer GaSe crystals.     

Dynamics of single-wall carbon nanotube synthesis by laser vaporization

The key spatial and temporal scales for single-wall carbon nanotube (SWNT) synthesis by laser vaporization at high temperatures are investigated with laser-induced luminescence imaging and spectroscopy. Graphite/(Ni, Co) targets are ablated under typical synthesis conditions with a Nd:YAG laser at 1000 °C in a 2-in. quartz tube reactor in flowing 500-Torr Ar. The plume of ejected material is followed for several seconds after ablation using combined imaging and spectroscopy of Co atoms, C₂ and C₃ molecules, and clusters. The ablation plume expands in stages during the first 200 7s after ablation and displays a self-focusing behavior. Interaction of the plume with the background gas forms a vortex ring which segregates and confines the vaporized material within a ~1-cm³ volume for several seconds. Using time-resolved spectroscopy and spectroscopic imaging, the time for conversion of atomic and molecular species to clusters was measured for both carbon (200 7s) and cobalt (2 ms) at 1000 °C. This rapid conversion of carbon to nanoparticles, combined with transmission electron microscopy analysis of the collected deposits, indicate that nanotube growth occurs over several seconds in a plume of mixed nanoparticles. By adjusting the time spent by the plume within the high-temperature zone using these in situ diagnostics, single-walled nanotubes of controlled (~100 nm) length were grown and the first estimate of a growth rate on single laser shots (0.2 7m/s) was obtained.     

Raman study of Fano interference in p‐type doped silicon

As the silicon industry continues to push the limits of device dimensions, tools such as Raman spectroscopy are ideal to analyze and characterize the doped silicon channels. The effect of inter‐valence band transitions on the zone center optical phonon in heavily p‐type doped silicon is studied by Raman spectroscopy for a wide range of excitation wavelengths extending from the red (632.8 nm) into the ultra‐violet (325 nm). The asymmetry in the one‐phonon Raman lineshape is attributed to a Fano interference involving the overlap of a continuum of electronic excitations with a discrete phonon state. We identify a transition above and below the one‐dimensional critical point (E = 3.4 eV) in the electronic excitation spectrum of silicon. The relationship between the anisotropic silicon band structure and the penetration depth is discussed in the context of possible device applications. Copyright © 2010 John Wiley & Sons, Ltd.     

In situ measurements and modeling of carbon nanotube array growth kinetics during chemical vapor deposition

Direct measurements of carbon nanotube growth kinetics are described based upon time-resolved reflectivity (TRR) of a HeNe laser beam from vertically aligned nanotube arrays (VANTAs) as they grow during chemical vapor deposition (CVD). Growth rates and terminal lengths were measured in situ for VANTAs growing during CVD between 535 °C and 900 °C on Si substrates with evaporated Al/Fe/Mo multi-layered catalysts and acetylene feedstock at different feedstock partial pressures. Methods of analysis of the TRR signals are presented to interpret catalyst particle formation and oxidation, as well as the porosity of the VANTAs. A rate-equation model is developed to describe the measured kinetics in terms of activation energies and rate constants for surface carbon formation and diffusion on the catalyst nanoparticle, nanotube growth, and catalyst over-coating. Taken together with the TRR data, this model enables basic understanding and optimization of growth conditions for any catalyst/feedstock combination. The model lends insight into the main processes responsible for the growth of VANTAs, the measured number of walls in the nanotubes at different temperatures, conditions for growth of single-wall carbon nanotube arrays, and likely catalyst poisoning mechanisms responsible for the sharp decline in growth rates observed at high temperatures. PACS  61.46.+w; 81.07.De; 81.16.Hc     

Magnetic phases of amorphous transition metal-metalloid alloys

Hysteresis loop and ac susceptibility measurements were performed on three series of amorphous alloys: (A_wB_1-w)₇₅P₁₆B₆Al₃, where (A, B) are (Fe, Ni), (Co, Ni) and (Fe, Mn). Upon cooling, low w alloys undergo paramagne t to spin glass transitions. Alloys with higher w first experience a Curie transition to a ferromagnetic state, and then a spin freezing transition to a spin glass state. the T dependence of the width of the ac hysteresis loop is used to determine the spin freezing transition temperature. A magnetic phase diagram is presented for each alloy series and the value of w required for ferromagnetism, w_C, is determined. When measured in the presence of small constant fields, the ac susceptibility of alloys with w just above w_C has maxima near both transition temperatures. The field and temperature dependences of the peaks are explained by scaling arguments, used to determine the critical exponent δ for the Curie transition, and suggest that a similar scaling law holds for the ferromagnet to spin glass transition.     

Magnetic phase diagram of amorphous (FexNil-x)75P16B6Al3 alloys

We have studied the temperature dependence of the magnetic response of amorphous (Fe_xNi_l-x)₇₅P₁₆B₆A$\text{l}$₃ ribbons to a small low frequency applied field. For x ? 0.16 we identify a paramagnet-spin glass transition. With 0.17 ? x ? 0.4 a paramagnet-ferromagnet transition is observed which is followed at lower T by a spin freezing phenomenon. A magnetic phase diagram is proposed and discussed in terms of recent theories.     

Cumulative and continuous laser vaporization synthesis of single wall carbon nanotubes and nanohorns

The conditions for the scaled synthesis of single wall carbon nanotubes (SWNTs) and single wall carbon nanohorns (SWNHs) by laser vaporization at high temperatures are investigated and compared using in situ diagnostics. An industrial Nd:YAG laser (600 W, 1–500 Hz repetition rate) with tunable pulse widths (0.5–50 ms) is utilized to explore conditions for high-yield production. High-speed videography (50000 frames/s) of the laser plume and pyrometry of the target surface are correlated with ex situ high resolution transmission electron microscopy analysis of the products for pure carbon targets and carbon/catalyst targets to understand the effects of the processing conditions on the resulting nanostructures. Carbon is shown to self-assemble into single-wall nanohorn structures at rates of ∼1 nm/ms, which is comparable to the catalyst-assisted SWNT growth rates. Two regimes of laser ablation, cumulative ablation by multiple pulses and continuous ablation by individual pulses, were explored. Cumulative ablation with spatially overlapping 0.5-ms pulses is favorable for the high yield and production rate of SWNTs at ∼6 g/h while continuous ablation by individual long laser pulses (∼20 ms) at high temperatures results in the highest yield of SWNHs at ∼10 g/h. Adjustment of the laser pulse width is shown to control SWNH morphology.