Production of biologically inert Teflon thin layers on the surface of allergenic metal objects by pulsed laser deposition technology

Allergic-type diseases are current nowadays, and they are frequently caused by certain metals. We demonstrated that the metal objects can be covered by Teflon protective thin layers using a pulsed laser deposition procedure. An ArF excimer laser beam was focused onto the surface of pressed PTFE powder pellets; the applied fluences were 7.5–7.7 J/cm². Teflon films were deposited on fourteen-carat gold, silver and titanium plates. The number of ablating pulses was 10000. Post-annealing of the films was carried out in atmospheric air at oven temperatures between 320 and 500 °C. The thickness of the thin layers was around 5 μm. The prepared films were granular without heat treatment or after annealing at a temperature below 340 °C. At 360 °C a crystalline, contiguous, smooth, very compact and pinhole-free thin layer was produced; a melted and re-solidified morphology was observed above 420 °C. The adhesion strength between the Teflon films and the metal substrates was determined. This could exceed 1–4 MPa depending on the treatment temperature. It was proved that the prepared Teflon layers can be suitable for prevention of contact between the human body and allergen metals and so for avoidance of metal allergy. Received: 12 June 2002 / Accepted: 13 June 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. E-mail: bhopp@physx.u-szeged.hu     

Chemical sensing with pulsed QC-DFB lasers operating at 15.6 micrometers

Pulsed thermoelectrically cooled QC-DFB lasers operating at 15.6 μm were characterized for spectroscopic gas sensing applications. A new method for wavelength scanning based on repetition rate modulation was developed. A non-wavelength-selective pyroelectric detector was incorporated in the sensor configuration giving the advantage of room-temperature operation and low cost. Absorption lines of CO₂ and H₂O were observed in ambient air, providing information about the concentration of these species. Received: 29 April 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-713/348-5686, E-mail: akoster@rice.edu     

Deep drilling of metals by femtosecond laser pulses

Results of recent investigations on deep drilling of metals by femtosecond laser pulses are reported. At high laser fluences, well above the ablation threshold, femtosecond lasers can drill deep, high-quality holes in metals without any post-processing or special gas environment. It is shown that for high-quality drilling of metals, the following processes are important: (1) laser-induced optical breakdown of air containing metal vapor and small metal particles (debris) generated by multi-pulse femtosecond laser ablation, (2) transformation of laser pulses into light filaments, and (3) low-fluence finishing. Received: 15 November 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +49-511/2788-100, E-mail: ch@lzh.de     

Effect of exposure to air on sheet resistance and phase composition of Co silicides annealed at a low temperature of 470 °C

Attention has been attracted to Co silicides due to their superior properties in deep-submicron integrated circuit technology. In this paper, the effect of exposure to air on the properties of Co silicides has been studied. Co films of 20-nm thickness were deposited onto polysilicon layers using Ar sputtering. After deposition, the samples were exposed to air at room temperature for different times, ranging from 0 to 48 h, before a rapid thermal annealing (RTA) at 470 °C. It is found that exposure to air significantly changes the sheet resistance (R_s) and the phase composition of the silicides. The sample exposed to air for 48 h has R_sof∼71 Ω/sq, which is about 10% lower than that for the sample annealed immediately. This is due to the fact that more Co₂Si phase and less CoSi phase are formed in the former sample. The mechanism can be attributed to the gases in air (e.g. O₂), which contaminate the Co/Si interface and act as a kinetic barrier during the subsequent RTA. It has been demonstrated that gaseous contamination from air strongly influences the CoSi_x phase transformation. Received: 3 June 2002 / Accepted: 29 June 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. E-mail: qiang.huang@philips.com     

Pressure-controlled preparation of nanocrystalline complex oxides using pulsed-laser ablation at room temperature

Nanocrystalline thin films of complex oxides such as BaTiO₃ and LaFeO₃ were prepared by pulsed laser ablation without substrate heating. Targets under various Ar pressures were irradiated using an ArF excimer laser. The off-axis configuration of targets and substrates was used to synthesize the films. The crystallinity and chemical composition of the deposited films were strongly dependent on the processing Ar gas pressure. In case of BaTiO₃, the film deposited at 10 Pa was a single phase of BaTiO₃ with a crystallite size around 7.2 nm. With increasing Ar pressure to 200 Pa, XRD peaks of BaTiO₃ as well as BaCO₃ were observed. The by-products could be due to reaction with carbon dioxide in air after taking the sample out of the chamber. For LaFeO₃, the films deposited under 50 to 200 Pa had a single phase with a crystallite size below 10 nm. When the Ar pressure exceeded 100 Pa, the crystallite size tended to decrease for both BaTiO₃ and LaFeO₃, which could be due to formation of aggregated nanoparticles. Below 10 Pa, oxygen deficiency was observed. Over 50 Pa, the atomic concentration of all the constituent elements was almost constant, especially the [Ba]/[Ti] and [La]/[Fe] ratios, which were nearly unity. Received: 19 June 2002 / Accepted: 24 June 2002 / Published online: 22 November 2002 RID="*" ID="*"Corresponding author. Fax: +81-298/61-6355, E-mail: yoon-jw@aist.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     

Sub-part-per-billion detection of nitric oxide in air using a thermoelectrically cooled mid-infrared quantum cascade laser spectrometer

Non-cryogenic, laser-absorption spectroscopy in the mid-infrared has wide applications for practical detection of trace gases in the atmosphere. We report measurements of nitric oxide in air with a detection limit less than 1 nmole/mole (<1 ppbv) using a thermoelectrically cooled quantum cascade laser operated in pulsed mode at 5.26 μm and coupled to a 210-m path length multiple-pass absorption cell at reduced pressure (50 Torr). The sensitivity of the system is enhanced by operating under pulsing conditions which reduce the laser line width to 0.010 cm^-1 (300 MHz) HWHM, and by normalizing pulse-to-pulse intensity variations with temporal gating on a single HgCdTe detector. The system is demonstrated by detecting nitric oxide in outside air and comparing results to a conventional tunable diode laser spectrometer sampling from a common inlet. A detection precision of 0.12 ppb Hz^-1/2 is achieved with a liquid-nitrogen-cooled detector. This detection precision corresponds to an absorbance precision of 1×10^-5 Hz^-1/2 or an absorbance precision per unit path length of 5×10^-10 cm^-1 Hz^-1/2. A precision of 0.3 ppb Hz^-1/2 is obtained using a thermoelectrically cooled detector, which allows continuous unattended operation over extended time periods with a totally cryogen-free instrument. Received: 1 May 2002 / Revised version: 6 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-978/663-4918, E-mail: ddn@aerodyne.com     

High-yield synthesis of multi-walled carbon nanotubes by arc discharge in liquid nitrogen

Synthesis of multi-walled carbon nanotubes (MWNTs) by arc discharge in liquid nitrogen is reported. As liquid nitrogen substituted both vacuum and cooling systems, high-quality MWNTs were produced at a low cost. The content of the MWNTs can be as high as 70% of the reaction product. Auger-spectroscopy analysis revealed that no nitrogen is incorporated in the MWNTs. This method can be an economical route for the mass production of highly crystalline MWNTs. Received: 5 July 2002 / Accepted: 8 July 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +82-54/279-8298, E-mail: ce20047@postech.ac.kr     

Investigation of the interaction of evaporated aluminum with vapor deposited Teflon AF films via X-ray photoelectron spectroscopy

The interfacial bonding and mixing between evaporated aluminum and a vapor deposited Teflon AF (abbreviated to AF) film have been investigated with X-ray photoelectron spectroscopy. Graphite carbon (C–C), and aluminum carbide (Al–C), oxide (Al–O–C) and fluoride (Al–F) are formed when aluminum atoms are deposited on to the AF film. With increasing deposition of aluminum, the concentrations of these newly formed components increase gradually. Moreover, in situ annealing results in remarkable increases in the C–C, Al–C, Al–O–C and Al–F configurations and a decrease in metallic aluminum. No significant diffusion of aluminum into the AF film was observed during the annealing. The Al compounds form a layer at the Al/AF interface that acts as an adhesion promoter and diffusion barrier. Received: 21 October 2002 / Accepted: 22 October 2002 / Published online: 15 January 2003 RID="*" ID="*"Corresponding author. Fax: +49-431/880-6229, E-mail: sjding@yahoo.com     

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     

Local fuel concentration measurements in internal combustion engines using spark-emission spectroscopy

Spectrally resolved visible and ultraviolet emissions are investigated as a basis for wide-range, individual-cycle measurement of the local fuel concentration in spark-ignition engines. The 388-nm CN emission intensity, normalized by the spark-discharge energy during the observation interval (typically 150 μs at the start of the glow discharge), is found to be the most useful measure of fuel concentration when data are required over a wide range. Calibration data for homogeneous propane–air and isooctane–air mixtures over a wide range of cylinder gas conditions at the time of ignition collapse to a single curve when the fuel concentration is expressed in terms of the number density of carbon atoms. The carbon number densities measured in this study correspond to fuel–air equivalence-ratios in the range 0–3 at 95% throttle conditions. Random and systematic errors are 10% or less. Applied to an engine in which liquid fuel is injected directly into the cylinder, the technique reveals substantial cyclic fluctuations in the fuel concentration at the spark gap for early fuel injection (intended to produce a homogeneous fuel–air mixture in the combustion chamber) and large fuel-concentration fluctuations for late fuel injection (which produces a highly stratified mixture). The results also show that for stratified operation with a fixed fuel-injection timing, a spark timing that is later than optimum leads to incomplete combustion in many cycles due to fuel–air ratios that are too lean for good ignition and rapid flame development. Received: 6 November 2001 / Revised version: 6 May 2002 / Published online: 25 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-586/986 0176, E-mail: todd.fansler@gm.com     

Tuning and stability of a continuous-wave mid-infrared high-power single resonant optical parametric oscillator

A 2.2-W continuous-wave, continuously tunable, single-frequency OPO has been developed in the 3.0–3.8 μm wavelength range for the detection of molecular trace gasses. The oscillation threshold, output power and stability of the single resonant OPO were improved by optimizing pump beam waist and OPO cavity length. Both air-spaced and solid etalons were tested to frequency stabilize and tune the OPO, from which the solid etalon gave a better performance. Temperature oscillations in the PPLN crystal caused oscillations in the idler wavelength of less than 200 MHz over 300 s; the short-term stability was less than 3 MHz over 1 s. The high laser power, in combination with photoacoustic spectroscopy, achieved a detection limit of 10 parts-per-trillion for ethane in nitrogen. Received: 9 April 2002 / Revised version: 14 June 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax:+31-24/3653311, E-Mail: maartenh@sci.kun.nl     

Spontaneous growth of arsenic oxide micro-crystals on chemically etched MnAs surfaces

Micrometer-size crystals are observed to grow spontaneously on chemically etched MnAs surfaces. The wet chemical etching leaves a nearly exclusive pile of amorphous arsenic on the surface when the MnAs layer is etched incompletely. Using Raman spectroscopy, we identify that these micro-crystals are the arsenolite crystal of arsenic oxides. The manganese in the MnAs layer is oxidized by the hydrogen peroxide in the etch solution to MnO₂, which then works as the catalyst for the rapid oxidation and crystallization of the amorphous arsenic. Received: 14 November 2002 / Accepted: 18 November 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. Fax: +49-30/20377-515, E-mail: takagaki@pdi-berlin.de     

The application of quasi-phase-matched parametric light sources to practical infrared chemical sensing systems

Quasi-phase-matched (QPM) materials allow the generation of spectroscopically useful infrared radiation in an efficient and broadly tunable format. Here, we describe several applications of QPM-based light sources to remote and local chemical sensing. The remote systems are gas imagers that employ a fiber-pumped continuous-wave optical parametric oscillator or a microlaser-pumped, diode-seeded optical parametric amplifier as the illumination source. Technology described for local sensing includes a cavity ring down spectrometer that employs a novel optical parametric generator–amplifier to achieve ≥350 cm^-1 of contiguous tuning and a long-wave infrared light source based on QPM GaAs. In each case the use of QPM materials in conjunction with effective pump sources instills simplicity and ruggedness into the sensing systems. Received: 15 April 2002 / Revised version: 6 June 2002 / Published online: 12 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-925/294-2595, E-mail: tjkulp@sandia.gov RID="**" ID="**"Present address: Corning Inc., Corning, NY 14831, USA RID="*" ID="*"Present address: Corning Inc., Corning, NY 14831, USA RID="**" ID="**"Present address: Blue Leaf Networks, Sunnyvale, CA 94086, USA RID="***" ID="***"Present address: Sandia National Laboratories, Albuquerque, NM 87185, USA     

Rapid formaldehyde monitoring in ambient air by means of mid-infrared cavity leak-out spectroscopy

We report the spectroscopic detection of formaldehyde in ambient air using cavity leak-out spectroscopy, a cw variant of cavity ring-down spectroscopy. This technique proved to be suitable for a real-time quantitative analysis of polluted air without any preprocessing of the air sample. Using a tunable CO-overtone sideband laser for the λ=3 μm spectral region and a ring-down cell with R=99.95% mirrors, we achieved a detection limit of 2 parts per billion formaldehyde in ambient air, corresponding to a minimum detectable absorption coefficient of 7×10^-9/cm (sampling time: 2 s). Calibration problems arising from the polarity of the molecule and due to HITRAN database uncertainties are discussed. Received: 28 March 2002 / Revised version: 7 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +49-211/811-3121, E-mail: muertz@uni-duesseldorf.de     

Simultaneous measurement of absolute OH concentration,temperature and flow velocity in a flame by photothermal deflection spectroscopy

We demonstrate the use of photothermal deflection spectroscopy for a simultaneous measurement of absolute minority-species concentration, temperature and flow velocity in a flame from the analysis of a single data trace. The ability to make absolute concentration measurements, as well as the ability to measure three important combustion parameters simultaneously, may make this technique quite useful in many circumstances. Received: 27 August 2002 / Revised version: 26 September 2002 / Published online: 11 December 2002 RID="*" ID="*"Corresponding author. Fax: +1-479/575-4580, E-mail: rgupta@uark.edu     

Interaction of two light beams with different polarizations in TGS

By ellipsometric measurements we have observed the polarization variations of the primary light beam, with wavelength λ₁=5145 ?, interacting with the secondary light beam of controlled variable polarization, transmitted through a TGS crystal layer. We present a theoretical explanation based on the second-order optical nonlinearity of TGS. Received: 4 December 2001 / Revised version: 28 May 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +48-22/660-5447, E-mail: petyk@if.pw.edu.pl     

Laser-based photoacoustic ammonia sensors for industrial applications

An industrial trace-ammonia sensor based on photoacoustic spectroscopy and CO₂ lasers has been developed for measuring ammonia with a 1σ detection limit of 220 parts-per-trillion (ppt) in an integration time of 30 s. The instrument response time for measuring ammonia was 200 s, limited by adsorption effects due to the polar nature of ammonia. The minimum detectable fractional absorbance was 2.0×10^-7, and the minimum normalized detectable absorption coefficient for this system was 2.4×10^-7 W cm^-1/z. The 9R(30) transition of the CO₂ laser at 9.22 μm with 2 W of output power was used to probe the strong sR(5,K) multiplet of ammonia at the same wavelength. This sensor was demonstrated with an optically multiplexed configuration for simultaneous measurement in four cells. Received: 3 April 2002 / Revised version: 31 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-310/458-0171, E-mail: webber@pranalytica.com     

Lasing action in air induced by ultra-fast laser filamentation

The backscattered fluorescence of nitrogen from filaments generated by intense ultra-fast Ti:sapphire laser pulses propagating in air is studied. The backscattered fluorescence from N₂ molecules and ions show an exponential increase with increasing filament length, indicating amplified spontaneous emission. Received: 11 October 2002 / Revised version: 3 December 2002 / Published online: 26 February 2003 RID="*" ID="*"Corresponding author. Fax: +1-418/6562-623, E-mail: qluo@phy.ulaval.ca     

Copper nanowire arrays for infrared polarizer

A micropolarizer of copper nanowire arrays within anodic alumina membrane (AAM) was fabricated by anodization of pure Al foil and electrodeposition of Cu, respectively. X-ray diffraction, scanning electron microscopy and transmission electron microscopy investigations reveal that the ordered Cu nanowires are essentially single crystal, and have an average diameter of 90 nm. Spectrophotometer measurements show that the copper nanowire arrays embedded in AAM can only transmit polarized light vertical to the wires. An extinction ratio of 24 to 32 dB and an average insertion loss of 0.5 dB in the wavelength range of 1 to 2.2 μm were obtained, respectively. Therefore Cu nanowire/AAM can be used as a wire grid type micropolarizer. Received: 28 January 2002 / Accepted:17 May 2002 / Published online: 22 November 2002 RID="*" ID="*"Corresponding author. Fax: +86-551/559-1434, E-mail: ytpang@263.net