Methane analyzer based on TDL’s for measurements in the lower stratosphere: design and laboratory tests

This paper describes a tunable diode laser spectrometer for the in situ measurement of methane by high-resolution absorption spectroscopy of roto-vibrational lines, using a distributed feedback laser emitting in the near infrared (1.65 μm) and a multi-pass cell, with a two-tone detection scheme. The instrument was designed to be installed on the high-altitude aircraft M55 Geophysica, for high-sensitivity and high-temporal-resolution measurement of CH₄, both as a greenhouse gas and as a tracer of air-mass motion. The instrument-design criteria to achieve the compactness, low weight, and ruggedness necessary for automatic operation on an unpressurized high-altitude aircraft are reported. Results of the laboratory testing are also shown and discussed. Received: 1 April 2002 / Revised version: 28 May 2002 / Published online: 12 September 2002 RID="*" ID="*"Corresponding author. Fax: +39-050/313-7597, E-mail: damato@scintec.it     

Quantitative analysis of dilute mixtures of SO<Subscript>2</Subscript> in N<Subscript>2</Subscript> at 7.4 μm by difference frequency spectroscopy

We describe a 7.4-μm source based on difference frequency generation with 6.5 mW of 1278-nm radiation from an extended cavity laser and 66 mW of 1544-nm radiation from another extended cavity laser, amplified in an erbium-doped fibre amplifier. Optimum focusing of the input beams in the 5×5×10-mm³ AgGaSe₂ crystal, and the spatial and temporal characteristics of the output beam, are determined. The source is used for accurate determination of line parameters for selected lines of the ν₃ band of SO₂, centred at 1361 cm^-1. Subsequently, these lines are used for performing quantitative analysis of gas mixtures containing SO₂ at concentration levels down to 4 ppm without relying on any calibration with certified gas mixtures. This demonstrates the potential of infrared spectroscopy as a primary method for low-concentration gas analysis. Received: 16 January 2003 / Revised version: 19 February 2003 / Published online: 9 April 2003 RID="*" ID="*"Corresponding author. Fax: +45-4593/1137, E-mail: jh@dfm.dtu.dk     

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     

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     

Application of mid-infrared cavity-ringdown spectroscopy to trace explosives vapor detection using a broadly tunable (6–8 μm) optical parametric oscillator

A novel instrument, based on cavity-ringdown spectroscopy (CRDS), has been developed for trace gas detection. The new instrument utilizes a widely tunable optical parametric oscillator (OPO), which incorporates a zinc–germanium–phosphide (ZGP) crystal that is pumped at 2.8 μm by a 25-Hz Er,Cr:YSGG laser. The resultant mid-IR beam profile is nearly Gaussian, with energies exceeding 200 μJ/pulse between 6 and 8 μm, corresponding to a quantum conversion efficiency of approximately 35%. Vapor-phase mid-infrared spectra of common explosives (TNT, TATP, RDX, PETN and Tetryl) were acquired using the CRDS technique. Parts-per-billion concentration levels were readily detected with no sample preconcentration. A collection/flash-heating sequence was implemented in order to enhance detection limits for ambient air sampling. Detection limits as low as 75 ppt for TNT are expected, with similar concentration levels for the other explosives. Received: 1 April 2002 / Revised version: 13 June 2002 / Published online: 12 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-408/524-0551, E-mail: mtodd@picarro.com     

A versatile photoacoustic spectrometer for sensitive trace-gas analysis in the mid-infrared wavelength region (5.1–8.0 and 2.8–4.1 μm)

A versatile CO laser-based photoacoustic spectrometer is presented equipped with three photoacoustic cells placed inside the laser cavity. The newly designed CO laser can operate both in the Δv=1 and the Δv=2 modes (5.1–8.0 μm and 2.8–4.1 μm) on 400 laser lines. Improved laser operation originating from a better cooling of the gas discharge was evidenced by a shift of the laser output power to lower J-values. Due to the wide emission range of the source, many molecules of biological and atmospheric interest, including methane and ethane, can be detected with sensitivities typically at the (sub)ppb level. Measurement of the respiration of a cockroach showed that the spectrometer is not only sensitive, but also has a good time response (8 s at a flow rate of 10 l/h). Received: 3 April 2002 / Revised version: 14 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Current address: Soegijapranata Catholic University, Department of Food Technology, Jalan Pawiyatan Luhur IV/1 Bendan Duwur, P.O. Box 8033/SM, Semarang 50234, Indonesia RID="**" ID="**"Current address: Sanata Dharma University, FMIPA, Kampus III, Paingan, Maguwoharjo, Depok, Sleman, Tromol Pos 29, Yogyakarta 55002, Indonesia RID="***" ID="***"Corresponding author. Fax: +31-24/365-3311, E-mail: fransh@ sci.kun.nl     

Generation of 100 μJ pulses at 82.8 nm by frequency tripling of sub-picosecond KrF laser radiation

. Investigations of the efficient generation of powerful coherent radiation at 82.8 nm by frequency tripling of short-pulse KrF laser radiation are presented. Argon gas is selected as nonlinear medium due to the resonantly enhanced 3rd-order susceptibility χ⁽³⁾(-3ω,ω,ω,ω). Pulse energies of 100 μJ at 82.8 nm have been measured for a pump pulse energy of 14 mJ. An upscaling to more than 500 μJ is expected with available more powerful pump lasers. Features of this XUV source and possible applications are discussed. Received: 26 July 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +49-511/7622211, E-mail: reinhardt@iqo.uni-hannover.de     

Efficient tunable laser operation of diode- pumped Yb,Tm:KY(WO4)2 around 1.9 μm

A new laser medium – Yb,Tm:KY(WO₄)₂ – for diode pumped solid state laser applications operating around 1.9 to 2.0 μm has been investigated and the main laser characteristics are presented. Diode pumping at 981 nm and around 805 nm was realised. For 981-nm pumping, the excitation occurs into Yb³⁺ ions followed by an energy transfer to Tm³⁺ions. A slope efficiency of 19% was realised. For pumping around 805 nm, the excitation occurs directly into the Tm³⁺ ions. Here a maximum slope efficiency of 52%, an optical efficiency of 40%, and output powers of more than 1 W were realised. Using a birefringent quartz plate as an intracavity tuning element, the tunability of the Yb,Tm:KY(WO₄)₂ laser in the spectral range of 1.85–2.0 μm has been demonstrated. The possibility of laser operation in a microchip cavity configuration for this material has also been shown. Received: 12 March 2002 / Revised version: 20 May 2002 / Published online: 25 September 2002 RID="*" ID="*"Corresponding author. Fax: +49-531/592-4116, E-mail: stefan.kueck@ptb.de     

Far-infrared laser emission from deuterated ammonia

By optically pumping the deuterated isotopomers of ¹⁴NH₃ and ¹⁵NH₃ using ¹²C¹⁶O₂, ¹³C¹⁶O₂, ¹²C¹⁸O₂, and ¹³C¹⁸O₂ lasers, several new far-infrared (FIR) emission lines between 65 μm and 125 μm have been detected. The existing spectroscopy of ¹⁴N-ammonia isotopomers has been used to identify many of these lines, as well as some previously observed but unidentified. The spectroscopic data have been analyzed to predict over 20 additional FIR laser lines that could be pumped by a more capable CO₂ laser. This effort was motivated by a need for strong laser lines in frequency coincidence with molecular transitions of astrophysical interest. Of particularnote is the measurement of the 2680-GHz line of ¹⁴NHD₂, whose frequency is 4.9 GHz higher than that of the important J=1-0 line of interstellar HD. Received: 25 July 2002 / Published online: 20 December 2002 RID="*" ID="*"Corresponding author. Fax: +1-303/492-5941, E-mail: boreiko@spot.colorado.edu     

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     

Trace-gas sensing in the 3.3-μm region using a diode-based difference-frequency laser photoacoustic system

A compact, diode-based difference-frequency laser system combined with a photoacoustic detection scheme is presented for trace-gas sensing. It features a broad, continuous tuning range (3.2–3.7 μm), a narrow line width (154 MHz), and room-temperature operation, and thus allows numerous gas species to be measured both isolated and in mixtures of different gases. Several trace-gas species of environmental interest were detected, and gas mixtures were analysed. The detection limits are in the low-ppmV range, e.g. 1.3 ppmV for methane, 1.8 ppmV for ethane, and 1.2 ppmV for hydrogen chloride. Received: 10 April 2002 / Revised version: 5 June 2002 / Published online: 12 September 2002 RID="*" ID="*"Corresponding author. Fax: +41-1/633-1077, E-mail: Sigrist@iqe.phys.ethz.ch     

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     

Photoacoustic gas sensing employing fundamental and frequency-doubled radiation of a continuously tunable high-pressure CO2 laser

We present the first photoacoustic spectrometer for gas sensing employing both the fundamental and the frequency-doubled radiation of a continuously tunable high-pressure CO₂ laser with room temperature operation. A quasi-phase-matched diffusion-bonded GaAs crystal is used in the system for second-harmonic generation. A pulsed photoacoustic detection scheme with a non-resonant cell, equipped with an 80-microphone array, is employed. The wide continuous tuning range in the fundamental (9.2–10.7 μm) and the frequency-doubled (4.6–5.35 μm) regimes, together with the narrow linewidth of 540 MHz (0.018 cm^-1) for the 10-μm region and of 1050 MHz (0.0315 cm^-1) for the 5-μm region, allow the measurement of gas mixtures, individual species and isotope discrimination. This is illustrated with measurements on NO and CO₂. The measured isotope ratio ¹⁵ NO/¹⁴ NO=(3.58±0.55)×10^-3 agrees well with the literature (3.700×10^-3) and demonstrates the good selectivity of the system. Received: 30 April 2002 / Revised version: 10 June 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax: +41-1/633-1077, E-mail: sigrist@iqe.phys.ethz.ch     

High-efficiency optical compression of Ti:sapphire laser pulses at 800 nm using a silver-coated hollow fiber

A 50 cm silver coated hollow fiber with inner diameter of 250 μm and filled with argon has been used to compress optical pulses from a Ti:sapphire laser at 800 nm. Input pulses with energy of 250 μJ and duration of 110 fs were used and compressed pulses with energy of 220 μJ and duration of 20 fs were generated by using a prism compressor. Numerical and experimental results are compared. There is good agreement between the measured beam diameters of the hollow-fiber output pulse and the calculated values obtained from propagation of the HE₁₁ mode into free space. For comparison, a similar uncoated fused-silica hollow fiber was also used to obtain 20 fs compressed pulses with an energy of 190 μJ. Received: 7 September 2002 / Published online: 26 March 2003 RID="*" ID="*"Corresponding author. Fax: +1-780/492-1811, E-mail: mohebbi@ee.ualberta.ca     

PbS-doped phosphate glasses saturable absorbers for 1.3-μm neodymium lasers

Passive mode locking and saturable absorber Q-switching of neodymium lasers at 1.3 μm with PbS-doped phosphate glasses are demonstrated. Q-switched pulses of 120 ns (0.1 μJ) in duration (energy) and the average output power of 3 mW from a quasi-cw diode-pumped Nd³⁺:KGW laser and ultrashort pulses of a maximum of 250 μJ in energy and 150 ps in duration from a Nd³⁺:YAP laser were obtained. The bleaching decay rate of the samples was found to increase with the Quantum Dot’s size decreasing due to the enhancement of quantum confinement effects for smaller dots and stronger overlapping of the electron and trap state wave functions. Received: 23 January 2002 / Revised version: 2 April 2002 / Published online: 20 December 2002 RID="*" ID="*"Corresponding author. Fax: +375-17/232-6286, E-mail: savitski@eudoramail.com     

Femtosecond pulse shaping in the mid infrared by difference-frequency mixing

The generation of programmable complex femtosecond pulses in the mid infrared (3–10 μm) with high precision is reported. Designed pulse shapes in the near infrared (1–1.6 μm) are transferred to the mid infrared via difference-frequency mixing with a second infrared pulse spectrally narrowed in a zero-dispersion compressor. In particular, pulse sequences with variable relative phases have been obtained. The control of the pulse properties is achieved purely electronically, allowing for implementation into a feedback loop. Received: 12 December 2003 / Published online: 3 April 2003 RID="*" ID="*"Corresponding author. Fax: +49-89/32905-200, E-mail: mcm@mpq.mpg.de     

13CO2/12CO2 isotopic ratio measurements using a difference frequency-based sensor operating at 4.35 micrometers

A portable modular gas sensor for measuring the ¹³C/¹²C isotopic ratio in CO₂ with a precision of 0.8‰(±1σ) was developed for volcanic gas emission studies. This sensor employed a difference frequency generation (DFG)-based spectroscopic source operating at 4.35 μm (∼2300 cm^-1) in combination with a dual-chamber gas absorption cell. Direct absorption spectroscopy using this specially designed cell permitted rapid comparisons of isotopic ratios of a gas sample and a reference standard for appropriately selected CO₂ absorption lines. Special attention was given to minimizing undesirable precision degrading effects, in particular temperature and pressure fluctuations. Received: 16 April 2002 / Revised version: 28 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-713/5245237, E-mail: fkt@rice.edu     

Development of a tunable mid-IR difference frequency laser source for highly sensitive airborne trace gas detection

The development of a compact tunable mid-IR laser system at 3.5 μm for quantitative airborne spectroscopic trace gas absorption measurements is reported. The mid-IR laser system is based on difference frequency generation (DFG) in periodically poled LiNbO₃ and utilizes optical fiber amplified near-IR diode and fiber lasers as pump sources operating at 1083 nm and 1562 nm, respectively. This paper describes the optical sensor architecture, performance characteristics of individual pump lasers and DFG, as well as its application to wavelength modulation spectroscopy employing an astigmatic Herriott multi-pass gas absorption cell. This compact system permits detection of formaldehyde with a minimal detectable concentration (1σ replicate precision) of 74 parts-per-trillion by volume (pptv) for 1 min of averaging time and was achieved using calibrated gas standards, zero air background and rapid dual-beam subtraction. This corresponds to a pathlength-normalized replicate fractional absorption sensitivity of 2.5×10^-10 cm^-1. Received: 29 April 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-303/497-1492, E-mail: dr@ucar.edu     

Femtosecond regenerative amplification in Cr:forsterite at 5–10 kHz

We developed a high-power oscillator–regenerative amplifier femtosecond laser system. Based on chromium-doped forsterite. The system is operating near 1.25 μm at a 5–10 kHz repetition rate. Chirped-pulse amplification produced 0.86 W (0.75 W) of average power, or 465 mW (400 mW) after compression at 5 kHz (10 kHz). Nearly bandwidth-limited pulses of duration 135 fs (shortest) and 150 fs (typical) are available with an energy of 93 μJ and 40 μJ at 5 and 10 kHz, respectively. Received: 7 June 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +49-30/63921289, E-mail: petrov@mbi-berlin.de     

Growth of a textured quasicrystalline phase in Ti-Ni-Zr films prepared by pulsed laser deposition

The preparation in thin film form of the known icosahedral phase in Ti-Ni-Zr bulk alloys has been investigated as a function of substrate temperature. Films were deposited by pulsed laser deposition on sapphire substrates at temperatures ranging from room temperature to 350 °C. Morphological and structural modifications have been followed by grazing-incidence and θ–2θ X-ray diffraction, transmission electron diffraction and imaging. Chemical composition has been analyzed by electron probe microanalysis. The in-depth variation of composition has been studied by secondary neutral mass spectroscopy. We show that pulsed laser deposition at 275 °C makes the formation of a 1-μm-thick film of Ti-Ni-Zr quasicrystalline textured nanocrystallites possible. Received: 7 June 2001 / Accepted: 18 February 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +33-3/8357-6300, E-mail: brien@mines.u-nancy.fr