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     

Simultaneous online detection of isoprene and isoprene-d2 using infrared photoacoustic spectroscopy

A photoacoustic spectrometer for the simultaneous detection of isoprene and the deuterated species [4,4-²H]-2-methyl-1,3-butadiene (isoprene-d₂) is presented. Using a sealed-off ¹³CO₂ laser a single-component detection limit of 400 ppt (isoprene) and 600 ppt (isoprene-d₂) was achieved. Simultaneous monitoring of both compounds allowed the detection of labelling levels down to 6% (isoprene-d₂ in total isoprene) with a time resolution of 3 min. In emission studies with Eucalyptus globulus, the deuterated precursor [4,4-²H]-1-deoxy-D-xylulose was fed to a leaf through the transpiration stream. Emission of isoprene-d₂ started as early as 10 min after application of the precursor. Received: 3 May 2002 / Revised version: 31 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +49-228/733474, E-mail: frank.kuehnemann@iap.uni-bonn.de     

Italian Renaissance and Hispano-Moresque lustre-decorated majolicas: imitation cases of Hispano-Moresque style in central Italy

An investigation was carried out on Renaissance lustre-decorated majolica shards, found during excavations made in Umbria (central Italy) and defined by experts, on the ground of the surface decoration, as imitations of the Hispano-Moresque style. A comparison between this particular kind of samples, produced in central Italy, and some Hispano-Moresque lustre shards has been performed. The ceramic bodies as well as the lustred surfaces have been analysed by means of several techniques: inductively coupled plasma optical emission spectrometry, X-ray diffraction (XRD), atomic absorption spectrometry with electrothermal atomisation and scanning electron microscopy. By means of XRD analysis the presence of cosalite (Pb₂Bi₂S₅) has been disclosed in the Italian lustre decorations but was not observed in the Hispano-Moresque ones. A hypothesis has been made, considering bismuth as a discriminating element, between lustres produced in central Italy and the Hispano-Moresque ones. We thought that the Italian artisans were able to manage the use of bismuth. Therefore a recipe, quite similar to the one employed by the Spanish artisans, was used by the Italian ceramists if their aim was to imitate the Hispano-Moresque style. Received: 4 November 2002 / Accepted: 6 November 2002 / Published online: 28 March 2003 RID="*" ID="*"Corresponding author. Fax: +39-06/9067-2316, E-mail: pad@mlib.cnr.it     

X-ray photoelectron spectroscopy study of magnetic films

Ta/NiO_x/Ni₈₁Fe₁₉/Ta films were prepared by rf reactive and dc magnetron sputtering. The exchange coupling field H_ex and the coercivity H_c of NiO_x/Ni₈₁Fe₁₉ as a function of the ratio of Ar to O₂ during the deposition process were studied. The composition and the chemical states in the interface region of NiO_x/NiFe were also investigated using X-ray photoelectron spectroscopy (XPS) and the peak decomposition technique. The results show that the ratio of Ar to O₂ has a great effect on the chemical states of nickel in NiO_x films. The exchange coupling field H_ex and the coercivity H_c of Ta/NiO_x/Ni₈₁Fe₁₉/Ta are thus seriously affected. XPS is shown to be a powerful tool for characterizing magnetic films. Received: 18 July 2001 / Accepted: 21 December 2001 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +86-010/6232-7283, E-mail: guanghua_yu@263.net     

High-speed vertical-cavity surface-emitting laser (VCSEL) absorption spectroscopy of ammonia (NH<Subscript>3</Subscript>) near 1.54 μm

A single-frequency VCSEL has been used for the first time for high-resolution spectroscopy near 1.5 μm. The incorporated buried-tunnel-junction technology enabled the realization of a long-wavelength InGaAlAs/InP VCSEL with low threshold current (0.925 mA), high output powers (0.576 mW) and low series resistance (60 Ω). The high-speed tuning capability of the long-wavelength VCSEL was investigated and used to conduct high-speed absorption spectroscopy. The peak tuning speed was measured to be 3.4 cm^-1/μs and a 4.5-cm^-1-wide NH₃ spectrum was recorded in 2 μs. The VCSEL was used to measure highly resolved low-pressure spectra for pressures ranging from 9.6 mbar to 1 bar. The measured Doppler-broadened linewidth of 0.02 cm^-1 agrees within 3% with the theoretical calculations. The availability and various advantages of 1.3–2-μm single-frequency VCSELs as compared to edge-emitting diode lasers, such as a large current tuning range even at very high tuning frequencies, and low production costs, should significantly expand the application fields for near-infrared laser gas sensors. Received: 17 July 2002 / Revised version: 4 December 2002 / Published online: 12 May 2003 RID="*" ID="*"Corresponding author. Fax: +43-1/58801-15999, E-mail: Gerhard@Totschnig.com     

Laser-induced etching and deposition of W using a-SiO<Subscript>2</Subscript> microspheres

A regular lattice of a-SiO₂ microspheres on a quartz support is used as a microlens array for laser-induced surface patterning by etching and deposition of W in atmospheres of WF₆ and WF₆+H₂, respectively. Received: 22 July 2002 / Accepted: 30 July 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +43-732/2468-9242, Email: dieter.baeuerle@jku.at     

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     

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     

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     

Study of range distribution parameters for bismuth-ion implantation in silver gallium diselenide

Range distributions for bismuth ions implanted in AgGaSe₂ in the energy range 80–300 keV were investigated by using 2.1-MeV He²⁺ Rutherford backscattering spectrometry (RBS). A convolution calculation method was used to extract the true distributions of bismuth from the measured RBS spectra. The range distribution parameters, R_p and ΔR_p, were obtained and compared with those obtained from Monte Carlo simulation. The experimental R_p values agree with the Monte Carlo simulation values very well, but the experimental ΔR_p values are systematically larger than those from the theoretical simulation. Received: 28 January 2002 / Accepted: 11 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-531/856-5167, E-mail: xdliu@sdu.edu.cn     

Sensitive absorption measurements in the near-infrared region using off-axis integrated-cavity-output spectroscopy

A novel instrument that employs a high-finesse optical cavity as an absorption cell has been developed for sensitive measurements of gas mixing ratios using near-infrared diode lasers and absorption-spectroscopy techniques. The instrument employs an off-axis trajectory of the laser beam through the cell to yield an effective optical path length of several kilometers without significant unwanted effects due to cavity resonances. As a result, a minimum detectable absorption of approximately 1.4×10^-5 over an effective optical path of 4.2 km was obtained in a 1.1-Hz detection bandwidth to yield a detection sensitivity of approximately 3.1×10^-11 cm^-1 Hz^-1/2. The instrument has been used for sensitive measurements of CO, CH₄, C₂H₂ and NH₃. Received: 6 May 2002 / Revised version: 31 May 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-650/965-7074, E-mail: d.baer@lgrinc.com     

Oxygen plasma and high pressure H<Subscript>2</Subscript>O vapor heat treatments used to fabricate polycrystalline silicon thin film transistors

Oxygen plasma and high pressure H₂O vapor heat treatment were applied to fabrication of n-channel polycrystalline silicon thin film transistors (poly-Si TFTs). 13.56 MHz-oxygen-plasma treatment at 250 °C, 100 W for 5 min effectively reduced defect states of 25-nm-thick silicon films crystallized by 30 ns-pulsed XeCl excimer laser irradiation. 1.3×10⁶-Pa-H₂O vapor heat treatment at 260 °C for 3 h was carried out in order to improve electrical properties of SiO_x gate insulators and SiO_x/Si interfaces. A carrier mobility of 470 cm²/V s and a low threshold voltage of 1.8 V were achieved for TFTs fabricated with crystallization at 285 mJ/cm². Received: 18 November 2002 / Accepted: 25 November 2002 / Published online: 11 April 2003 RID="*" ID="*"Corresponding author. Fax: +81-42/388-7109, E-mail: tsamesim@cc.tuat.ac.jp     

WS<Subscript>2</Subscript> layer formation on multi-walled carbon nanotubes

Time-dependent powder X-ray-diffraction analyses reveal that the conversion of WO₃ into WS₂ on carbon nanotube surfaces in the presence of H₂S is a one-step process. The WS₂ layers grow simultaneously along the tube in the radial and axial directions. Received: 17 June 2002 / Accepted: 19 June 2002 / Published online: 15 January 2003 RID="*" ID="*"Corresponding author. Fax: +44-1273/677-196, E-mail: d.walton@sussex.ac.uk     

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     

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     

Laser-induced fluorescence detection of acetylene in low-pressure propane and methane flames

Laser-induced fluorescence is used to detect and record profiles of acetylene formed as an intermediate species in 10-Torr premixed propane and methane flames. In low-temperature regions of the flames, excitation spectra confirm acetylene as the spectral carrier. The spectra of acetylene overlap those of O₂ and NO in terms of both excitation and detection wavelengths, however, acetylene can be detected with relatively little interference in the vicinity of 228 nm, using a detection wavelength of 260 nm. The fluorescence lifetime of acetylene in the flame conditions studied is approximately 20 ns, much shorter than the radiative lifetime, due to a high quenching rate for all the colliders investigated. This can be exploited in low-pressure flames to avoid interference from acetylene in monitoring nitric oxide. The acetylene mole fraction in propane flames reaches its peak value at nearly the same location as that of HCO, slightly closer to the burner than the peak CH mole fraction. The acetylene fluorescence signal is easily detected in propane flames over equivalence ratios from 0.6 to 1.2, although it increases under fuel-rich conditions. In methane flames, the acetylene signal is much weaker and is undetectable for fuel-lean conditions. Received: 5 August 2002 / Revised version: 30 September 2002 / Published online: 20 December 2002 RID="*" ID="*"Corresponding author. Fax: +1-202/767-1716, E-mail: brad@code6185.nrl.navy.mil     

Ultrahigh-efficiency TEM<Subscript>00</Subscript> diode-side-pumped Nd:YVO<Subscript>4</Subscript> laser

Ultrahigh-efficiency TEM₀₀ operation is demonstrated in a diode-pumped Nd:YVO₄ laser in a bounce amplifier geometry using a specially designed astigmatically optimised cavity configuration. Optical efficiency >68% is demonstrated and up to 27.1 W of output power for multimode operation. For single-mode TEM₀₀ operation, an output power of 23.1 W for 39.5 W of diode pumping was produced with beam propagation parameters of M_x ²=1.3 and M_y ²=1.1. Received: 10 October 2002 / Revised version: 9 December 2002 / Published online: 19 March 2003 RID="*" ID="*"Corresponding author. Fax: +44-20/7594-7744, E-mail: a.minassian@ic.ac.uk     

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     

Detection of N2O by photoacoustic spectroscopy with a compact, pulsed optical parametric oscillator

A pulsed optical parametric oscillator (OPO) operated in an optical cavity with a grazing-incidence grating configuration (GIOPO) was used for sensitive photoacoustic detection of trace quantities of dinitrogen oxide (N₂O). The (ν₁+ν₃) combination vibration band of N₂O was excited with the idler beam of the GIOPO at 2.86 μm using an optical cavity optimized for the idler beam. The linewidth of the GIOPO could be reduced to 0.4 cm^-1, allowing the rotational structure of the absorption spectrum to be resolved. A concentration sensitivity (signal-to-noise ratio=3) of 60 parts in 10⁹ by volume (60 ppb V) N₂O in synthetic air was obtained. This may be sufficient for continuous monitoring of N₂O in the atmosphere. Received: 29 April 2002 / Revised version: 4 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +49-6221/54-4255, E-mail: peter.hess@urz.uni-heidelberg.de