Electronic properties of Gd@C<Subscript>82</Subscript> metallofullerene peapods: (Gd@C<Subscript>82</Subscript>)<Subscript>n</Subscript>@SWNTs

Electronic properties of Gd@C₈₂ metallofullerene peapods, (Gd@C₈₂)_n@SWNTs, were investigated by electron energy-loss spectroscopy (EELS), scanning tunneling microscopy and spectroscopy (STM/STS), and field-effect transistor (FET) transport measurements. The results indicate that the electronic structure of Gd@C₈₂ metallofullerene peapods is completely different from that of intact single-walled nanotubes (SWNTs). For example, Gd@C₈₂-peapod-FETs show ambipolar behavior which is not observed in the empty SWNT-FETs under our experimental conditions. Furthermore, in semiconducting nanotubes the band gap can be varied from ∼0.5 to ∼0.1 eV using inserted Gd@C₈₂ endohedral metallofullerenes with a spatial periodicity of 1.1 to 8.0 nm, depending on the density of the fullerenes. The present findings suggest that metallofullerene peapods may point the way toward novel electronic devices. Received: 6 September 2002 / Accepted: 25 October 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-52/789-1169, E-mail: noris@cc.nagoya-u.ac.jp     

Low-threshold field electron emission of Si micro-tip arrays produced by laser ablation

Low-threshold field electron emission (FEE) is reported for periodic arrays of micro-tips produced by laser ablation of Si wafers. The best samples show emission at threshold fields as low as 4–5 V/μm for n-type Si substrates and of 1–2 V/μm for p-doped Si substrates, as measured with a flat-screen technique. Auger electron spectroscopy and X-ray electron spectroscopy reveal island-like deviation of the SiO₂ stoichiometry on the tip surfaces, with lateral dimensions of less than 100 nm. Microscopic studies using a special field-emission STM show that the emission originates from well-conducting regions of sub-micron size. The experimental data suggest FEE from the tip arrays by a geometric field enhancement of both the individual micro-tip and the narrow conducting channels in the tip body. Received: 3 May 2002 / Accepted: 1 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +7-095/135-82-34, E-mail: shafeev@kapella.gpi.ru     

Filling boron nitride nanotubes with metals

The authors’ endeavors over the last few years with respect to boron nitride (BN) nanotube metal filling are reviewed. Mo clusters of 1–2 nm in size and FeNi Invar alloy (Fe ∼60 at. %; Ni ∼40 at. %) or Co nanorods of 20–70 nm in diameter were embedded into BN nanotube channels via a newly developed two-stage process, in which multi-walled C nanotubes served as templates for the BN multi-walled nanotube synthesis. During cluster filling, low-surface-tension and melting-point Mo oxide first filled a C nanotube through the open tube ends, followed by fragmentation of this filling into discrete clusters via O₂ outflow and C→BN conversion within tubular shells at high temperature. During nanorod filling, C nanotubes containing FeNi or Co nanoparticles at the tube tips were first synthesized by plasma-assisted chemical vapor deposition on FeNi Invar alloy or Co substrates, respectively, and, then, the nanomaterial was heated to the melting points of the corresponding metals in a flow of B₂O₃ and N₂ gases. During this second stage, simultaneous filling of nanotubes with a FeNi or Co melt through capillarity and chemical modification of C tubular shells to form BN nanotubes occurred. The synthesized nanocomposites were analyzed by scanning and high-resolution transmission electron microscopy, electron diffraction, electron-energy-loss spectroscopy and energy-dispersive X-ray spectroscopy. The nanostructures are presumed to function as ‘nanocables’ having conducting metallic cores (FeNi, Co, Mo) and insulating nanotubular shields (BN) with the additional benefit of excellent environmental stability. Received: 10 October 2002 / Accepted: 25 October 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-298/51-6280, E-mail: golberg.dmitri@nims.go.jp     

Characterization of laser-ablated and chemically reduced silver colloids in aqueous solution by UV/VIS spectroscopy and STM/SEM microscopy

Silver colloids in aqueous solution were studied by different scanning microscopy techniques and UV/VIS spectroscopy. The silver colloids were produced either by chemical reduction or by nanosecond laser ablation from a solid silver foil in water. Variation of laser power and ablation time leads to solutions of metal clusters of different sizes in water. We characterized the electronic absorption of the clusters by UV/VIS spectroscopy. STM (scanning tunneling microscope) imaging of the metal colloids shows atomic resolution of rod- or tenon-like silver clusters up to 10-nm length formed by laser ablation. Our scanning electron microscope measurements, however, show that much larger silver colloids up to 5-μm length are also formed, which are not visible in the STM due to their roughness. We correlate them with the long-wavelength tail of the multimodal UV/VIS spectrum. The silver colloids obtained by chemical reduction are generally larger and their electronic spectra are red-shifted compared to the laser-ablated clusters. Irradiation of the colloid solution with nanosecond laser pulses of appropriate fluence at 532 nm and 355 nm initially reduced the colloid size. Longer irradiation at 355 nm, however, leads to the formation of larger colloids again. There seems to be a critical lower particle size, where silver clusters in aqueous solution become unstable and start to coagulate. Received: 24 June 2002 / Revised version: 25 July 2002 / Published online: 25 October 2002 RID="*" ID="*"This work is part of the thesis of H. M?ltgen RID="**" ID="**"Corresponding author. Fax: +49-211/811-5195, E-mail: kleinermanns@uni-duesseldorf.de     

The synthesis of highly oriented GaN nanowire arrays

Highly oriented GaN nanowire arrays have been achieved by the catalytic reaction of gallium with ammonium. The resulting materials were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM) and selected-area electron diffraction (SAED). SEM images show that the resulting materials are nanowire arrays with a uniform length of about 10 μm. XRD, EDS, TEM and SAED indicate that the nanowire arrays are single-crystal hexagonal GaN with a wurtzite structure. They have diameters of 10 to 20 nm. Received: 2 October 2002 / Accepted: 7 October 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. E-mail: wwwangjc@sina.com     

Structure and properties of TiO<Subscript>2</Subscript> surfaces: a brief review

Titanium oxides are used in a wide variety of technological applications where surface properties play a role. TiO₂ surfaces, especially the (110) face of rutile, have become prototypical model systems in the surface science of metal oxides. Reduced TiO₂ single crystals are easy to work with experimentally, and their surfaces have been characterized with virtually all surface-science techniques. Recently, TiO₂ has also been used to refine computational ab initio approaches and to calculate properties of adsorption systems. Scanning tunneling microscopy (STM) studies have shown that the surface structure of TiO₂(110) is more complex than originally anticipated. The reduction state of the sample, i.e. the number and type of bulk defects, as well as the surface treatment (annealing in vacuum vs. annealing in oxygen), can give rise to different structures, such as two different (1×2) reconstructions, a ‘rosette’ overlayer, and crystallographic shear planes. Single point defects can be identified with STM and influence the surface chemistry in a variety of ways; the adsorption of water is discussed as one example. The growth of a large number of different metal overlayers has been studied on TiO₂(110). Some of these studies have been instrumental in furthering the understanding of the ‘strong metal support interaction’ between group-VIII metals and TiO₂, as well as low-temperature oxidation reactions on TiO₂-supported nanoscopic gold clusters. The growth morphology, interfacial oxidation/reduction reaction, thermal stability, and geometric structure of ultra-thin metal overlayers follow general trends where the most critical parameter is the reactivity of the overlayer metal towards oxygen. It has been shown recently that the technologically more relevant TiO₂ anatase phase can also be made accessible to surface investigations. Received: 4 March 2002 / Accepted: 20 October 2002 / Published online: 5 February 2003 RID="*" ID="*"Corresponding author. Fax: +1-504/862-8279, E-mail: diebold@tulane.edu     

A simple wet-chemical synthesis and characterization of CuO nanorods

Using a simple wet-chemical route, we synthesized CuO nanorods with diameters of ca. 5–15 nm and lengths of up to 400 nm. The purity, crystallinity, morphology, structure features, and chemical composition of the as-prepared CuO nanorods were investigated by powder X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. Received: 22 March 2002 / Accepted: 12 June 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +86-25/359-5535, E-mail: wangqun@nju.edu.cn     

Large-scale synthesis of SnO2 nanobelts

Tin dioxide (SnO₂) nanobelts have been successfully synthesized in bulk quantity by a simple and low-cost process based on the thermal evaporation of tin powders at 800 °C. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations reveal that the nanobelts are uniform, with lengths from several-hundred micrometers to a few millimeters, widths of 60 to 250 nm and thicknesses of 10 to 30 nm. X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX) and selected-area electron diffraction analysis (SAED) indicate that the nanobelts are tetragonal rutile structure of SnO₂. The SnO₂ nanobelts grow via a vapor–solid (VS) process. Received: 3 June 2002 / Accepted: 10 June 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-551/559-1434, E-mail: gwmeng@mail.issp.ac.cn     

On the initiation of chemical reactions by electronic excitations in molecular solids

In this article we briefly review the results of theoretical simulations for the initiation of chemistry processes in high-explosive crystals from a solid-state-physics viewpoint. We analyze the possibility of initiation of chemical reactions from excited electronic states. In other words, we look for conditions that facilitate electronic excitations in the crystal. Specifically, we describe modifications to the electronic structure of RDX (cyclotrimethylene trinitramine) induced by lattice defects and by a shock wave traversing the solid. Our approach is based on ab initio Hartree–Fock band-structure calculations with electronic correlation corrections. An excitonic mechanism and a hole model, suggested earlier, are discussed in connection with the most recent experimental and theoretical advances in ultrafast optical techniques. We also consider here possible new avenues in the development of detonation theory. Received: 3 December 2001 / Accepted: 9 July 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +1-301/744-4451, E-mail: KuklaMM@ih.navy.mil     

Dielectric breakdown of rubber materials by femtosecond irradiation

We report the reversible micro-structuring of a synthetic rubber polymer (cis1,4-polybutadiene (PB)) by femtosecond laser illumination. Visco-elastic relaxation of the optically damaged region was observed. The recovery time, typically 10²–10⁴ ms, can be varied by changing the irradiation pulse energy. Multi-shot-induced damage recovers on the much longer scale of 10¹–10² s. It was found that the doping of PB by 4 wt. % of pentazadiene ([4-NO₂]–phenyl–N=N–N(C₃H₇)–N=N–phenyl–[4-NO₂]) reduces the threshold of light-induced photo-modification by 20%. This is explained by photo-induced (homolytic) cleavage of the pentazadiene bonds and formation of gaseous N₂, which facilitates material failure at the irradiated spot. The recovery of optical transmission can be applied to optical memory, optical and micro-mechanical applications. The underlying mechanism of the phenomenon is discussed in terms of anelastic α- and β-relaxation (polymer backbone and chains/coils relaxation, respectively). Received: 11 October 2001 / Accepted: 9 July 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +81-88/656-7598, E-mail: misawa@eco.tokushima-u.ac.jp     

High-resolution electron microscopy of individual metallofullerene molecules on the dipole orientations in peapods

Electron microscopy with atomic sensitivity enables us to obtain a direct image of the intra-molecular structure of metallofullerenes encapsulated inside single-walled carbon nanotubes. By a comparison of high-resolution images with a simulation to extract the relative atom positions for encaged metal atoms in each molecule, the distribution of the molecular orientations and interactions between adjacent molecules in metallofullerene peapods have been statistically analyzed. The results are suggestive of strong interactions between fullerene–fullerene and fullerene–tube in peapods at room temperature. Received: 10 October 2002 / Accepted: 25 October 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-298/61-6310, E-mail: suenaga-kazu@aist.go.jp     

High dynamic range optical limiting in fullerene doped porous glasses

A diffusion-controlled technique of obtaining gradient in molecular distribution of C₆₀ molecules in porous vycor glass is presented. Here toluene solution of C₆₀ is allowed to diffuse only in one-dimension. The molecular distribution in the doped glass is measured by transmission method. By comparing optical limiting performance in the graded and uniformly doped glasses, we show that there is about 10-fold increase in the dynamic range in graded device. Received: 10 July 2001 / Accepted: 11 January 2002 / Published online: 3 May 2002 RID="*" ID="*"Corresponding author. E-mail: mukesh@cat.ernet.in     

Laser-driven vehicles – from inner-space to outer-space

Laser-supported propulsion of a micro-airplane with a water-covered ablator is demonstrated. The repetitive use of an overlay structure is experimentally demonstrated with a specially designed water supply. Various transparent overlays are investigated by the CIP-based hydrodynamic code and by experiments using a pendulum and using a semi-conductor load cell. A momentum-coupling efficiency of ∼10⁴ N s/MJ is achieved by water–exotic-target experiments, in agreement with the simulation code, which predicts a maximum efficiency of ∼10⁵ N s/MJ. The concept of laser-supported propulsion can also be used for driving a Mach 5 airplane in the stratosphere, a micro-ship inside the human body, and a robot in a nuclear power reactor accident, during which large numbers of neutrons make electronic devices useless. Received: 7 October 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +81-3/5734-2165, E-mail: yabe@mech.titech.ac.jp     

Wavelength-agile fiber laser using group-velocity dispersion of pulsed super-continua and application to broadband absorption spectroscopy

A swept-wavelength source is created by connecting four elements in series: a femtosecond fiber laser at 1.56 μm, a non-linear fiber, a dispersive fiber and a tunable spectral bandpass filter. The 1.56-μm pulses are converted to super-continuum (1.1–2.2 μm) pulses by the non-linear fiber, and these broadband pulses are stretched and arranged into wavelength scans by the dispersive fiber. The tunable bandpass filter is used to select a portion of the super-continuum as a scan-wavelength output. A variety of scan characteristics are possible using this approach. As an example, an output with an effective linewidth of approximately 1 cm^-1 is scanned from 1350–1550 nm every 20 ns. Compared to previous scanning benchmarks of approximately 1 nm/μs, such broad, rapid scans offer new capabilities: a gas sensing application is demonstrated by monitoring absorption bands of H₂O, CO₂, C₂H₂ and C₂H₆O at a pressure of 10 bar. Received: 5 August 2002 / Revised version: 23 September 2002 / Published online: 22 November 2002 RID="*" ID="*"Corresponding author. Fax: +1-608/265-2316, E-mail: ssanders@engr.wisc.edu     

Fundamental limits for coherent manipulation on atom chips

The limitations for the coherent manipulation of neutral atoms with fabricated solid-state devices, so-called ‘atom chips’, are addressed. Specifically, we examine the dominant decoherence mechanism, which is due to the magnetic noise originating from the surface of the atom chip. It is shown that the contribution of fluctuations in the chip wires at the shot-noise level is not negligible. We estimate the coherence times and discuss ways to increase them. Our main conclusion is that future advances should allow for coherence times as long as 1 s, a few μm away from the surface. Received: 22 August 2002 / Revised version: 30 October 2002 / Published online: 26 February 2003 RID="*" ID="*"Corresponding author. E-mail: carsten.henkel@quantum.physik.uni-potsdam.de     

Wetting and scanning force microscopy on rough polymer surfaces: Wenzel’s roughness factor and the thermodynamic contact angle

The influence of the surface roughness of polypropylene on the contact angle hysteresis is investigated by means of ethylene glycol drops in order to estimate the true Young’s equilibrium contact angle. A new relationship between the contact angle hysteresis and Wenzel’s contact angle is derived. In addition, the determination of Wenzel’s roughness factor by means of scanning force microscopy opens an alternative way to obtaining Young’s equilibrium contact angle without any surface manipulation. The experimental results presented verify this new approach. Received: 2 September 2002 / Accepted: 2 September 2002 / Published online: 5 March 2003 RID="*" ID="*"Corresponding author. Fax: +49-3328/352-452, E-mail: helmut.kamusewitz@gkss.de     

X-ray photoelectron spectroscopy and near-edge X-ray-absorption fine structure of C60 polymer films

We report core-level and valence-band X-ray photoelectron spectroscopy (XPS) and carbon [ _]K near-edge X-ray-absorptionfine structure spectroscopy (NEXAFS) results of plasma-polymerized C₆₀. In comparison with evaporated C₆₀ the C 1s peak is broader and asymmetric for the C₆₀ polymer and its shake-up satellites diminished. Furthermore, the features of the valence-band as well as the features of the π^* antibonding orbitals of the C₆₀ polymer are broader and reduced in intensity. Changes in the electronic structure are attributed to the polymerization of C₆₀, the post-plasma functionalization of the surface by oxygen after exposure to atmosphere, and the occurrence of amorphous carbon. Received: 28 May 1999 / Accepted: 31 August 1999 / Published online: 8 March 2000     

Progress in the understanding of the normal state of the cuprates

Over the last years there has been increasing evidence that the normal state of the cuprates can not be described adequately with individual quasiparticles within Fermi-liquid theory. While the low-lying excitations in the superconducting state are nevertheless possibly of quasiparticle character, this character vanishes with the loss of superconducting phase coherence when going to the normal conducting state. Generally, this normal state is characterized by strong heterogeneity. In real space this manifests in charge and spin ordering, either static or dynamical, the so-called ‘stripes’. The spectral signatures of various models describing this unusual metallic normal state together with less exotic non-Fermi-liquid models, like the marginal Fermi liquid, will be compared to photoemission spectra with high angular and energy resolution and to results obtained by other methods. Received: 19 March 2002 / Accepted: 2 October 2002 / Published online: 5 February 2003 RID="*" ID="*"Corresponding author. Fax: +49-30/2093-7729, E-mail: christoph.janowitz@physik.hu-berlin.de     

Thermal tuning and modulation of a DFB fibre laser with a thin-film heater

Results are given for thermal tuning and modulation of a 1556-nm distributed feedback fibre laser by resistive heating of a thin silver film chemically deposited on the fibre. Without reaching the limits of performance, linear tuning is demonstrated at a rate of 1.72 pm/mW up to about 200 pm, and a peak-to-peak modulation of 100 MHz up to modulation frequencies of 60 Hz. The heat flow is analyzed, and the coated fibre is characterized in terms of the static and dynamic wavelength response to the applied electric power. The performance of the scheme is tested by recording part of the ν₁+ν₃ combination band spectrum of ¹³C₂H₂ with thermal modulation and scanning of the fibre laser. Received: 12 March 2002 / Revised version: 24 June 2002 / Published online: 25 September 2002 RID="*" ID="*"Corresponding author. Fax: +45/4593-1137, E-mail: sus@dfm.dtu.dk     

Development of a cw-laser-based cavity-ringdown sensor aboard a spacecraft for trace air constituents

The progress in the development of a sensor for the detection of trace air constituents to monitor spacecraft air quality is reported. A continuous-wave (cw), external-cavity tunable diode laser centered at 1.55 μm is used to pump an optical cavity absorption cell in cw-cavity ringdown spectroscopy (cw-CRDS). Preliminary results are presented that demonstrate the sensitivity, selectivity and reproducibility of this method. Detection limits of 2.0 ppm for CO, 2.5 ppm for CO₂, 1.8 ppm for H₂O, 19.4 ppb for NH₃, 7.9 ppb for HCN and 4.0 ppb for C₂H₂ are calculated. Received: 3 April 2002 / Revised version: 3 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-202/994-5873, E-mail: Houston@gwu.edu