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     

Off-axis continuous-wave cavity-enhanced absorption spectroscopy of narrow-band and broadband absorbers using red diode lasers

We present an application of continuous-wave (cw) cavity-enhanced absorption spectroscopy (CEAS) with off-axis alignment geometry of the cavity and with time integration of the cavity output intensity for detection of narrow-band and broadband absorbers using single-mode red diode lasers at λ=687.1 nm and λ=662 nm, respectively. Off-axis cw CEAS was applied to kinetic studies of the nitrate radical using a broadband absorption line at λ=662 nm. A rate constant for the reaction between the nitrate radical and E-but-2-eneof (3.78±0.17)×10^-13 cm³ molecule^-1 s^-1 was measured using a discharge-flow system. A nitrate-radical noise-equivalent (1σ≡ root-mean-square variation of the signal) detection sensitivity of 5.5×10⁹ molecule cm^-3 was achieved in a flow tube with a diameter of 4 cm and for a mirror reflectivity of ∼99.9% and a lock-in amplifier time constant of 3 s. In this case, a noise-equivalent fractional absorption per one optical pass of 1.6×10^-6 was demonstrated at a detection bandwidth of 1 Hz. A wavelength-modulation technique (modulation frequency of 10 kHz) in conjunction with off-axis cw CEAS has also been used for recording 1f- and 2f-harmonic spectra of the ^RR(15) absorption of the b¹Σ_g ⁺-X³Σ_g ^- (1,0) band of molecular oxygen at =14553.947 cm^-1. Noise-equivalent fractional absorptions per one optical pass of 1.35×10^-5, 6.9×10^-7 and 1.9×10^-6 were obtained for direct detection of the time-integrated cavity output intensity, 1f- and 2f-harmonic detection, respectively, with a mirror reflectivity of ∼99.8%, a cavity length of 0.22 m and a detection bandwidth of 1 Hz. Received: 24 June 2002 / Revised version: 12 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: vlk@physchem.ox.ac.uk     

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     

Electrooptic properties of lithium niobate crystals for extremely high external electric fields

The electrooptic effect in lithium niobate crystals (LiNbO₃) for extremely high externally applied electric fields of up to 65 kV/mm is investigated. Homogeneous electrooptic refractive-index changes of up to 4.8×10^-3 are found for ordinarily polarized light. No quadratic electrooptic effect is observed. An upper bound for the quadratic electrooptic coefficient of |s₁₃|≤2.3×10^-21 m²/V² is determined. Electrooptic, angular, and wavelength tuning of the Bragg condition of a thermally fixed hologram are demonstrated. Received: 29 October 2002 / Revised version: 14 January 2003 / Published online: 26 March 2003 RID="*" ID="*"Corresponding author. E-mail: ml@uni-bonn.de     

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     

Passive Q-switching of 1.44 μm and 1.34 μm diode-pumped Nd:YAG lasers with a V:YAG saturable absorber

Spectroscopic data of a V³⁺:YAG passive Q-switch crystal were measured. The absorption recovery time was determined to be of 37±7 ns and the ground state absorption cross section was estimated to be 0.7×10^-18 cm² at 1.44 μm and 3.5×10^-18 cm² at 1.34 μm. Passively Q-switched operation of diode pumped 1.44 μm and 1.3 μm Nd:YAG lasers was demonstrated using this crystal as saturable absorber. Average output powers of 1.42 W (1.44 μm) and 1.56 W (1.34 μm) and pulse energies of 24 μJ (1.44 μm) and 25 μJ (1.34 μm) were observed, respectively. Received: 19 August 2002 / Published online: 12 February 2003 RID="*" ID="*"Corresponding author. Fax: +49-40/42838-6281, E-mail: kretschmann@physnet.uni-hamburg.de     

Three-dimensional structuring of sapphire by sequential He+ ion-beam implantation and wet chemical etching

We present a method for the selective two- and three-dimensional patterning of sapphire using light ion-beam implantation to generate severe lattice damage to depths exceeding 1 μm and subsequent selective wet chemical etching of the damaged regions by hot H₃PO₄. C-cut sapphire crystals were implanted through contact masks using ion fluences of 1×10¹⁶ to 5×10¹⁷ He⁺/cm² and energies up to 400 keV. The etching process is characterized by a high selectivity and a rate of approximately 19 nm/min. Whereas an implantation that produces a continuously damaged pathway results in complete etching from the surface, sole in-depth implantation using only high-energy ions leads to under-etching of the crystalline surface layer. By a combination of these processes we have fabricated three-dimensional structures such as channels and bridges in sapphire. Received: 14 October 2002 / Accepted: 15 October 2002 / Published online: 26 February 2003 RID="*" ID="*"Corresponding author. Fax +41-21/693-3701, E-mail: aurelian.crunteanustanescu@epfl.ch     

N+BF<Subscript>2</Subscript> and N+C+BF<Subscript>2</Subscript> high-dose co-implantation in silicon

Nitrogen and boron BF₂, and nitrogen, carbon, and boron BF₂ high-dose (6×10¹⁶–3×10¹⁷ cm^-2) co-implantation were performed at energies of about 21–77 keV. Subsequent high-temperature annealing processes (600, 850, and 1200 °C) lead to the formation of three and two surface layers respectively. The outer layer mainly consists of polycrystalline silicon and some amorphous material and Si₃N₄ inclusions. The inner layer is highly defective crystalline silicon, with some inclusions of Si₃N₄ too. In the N+B-implanted sample the intermediate layer is amorphous. Co-implantation of boron with nitrogen and with nitrogen and carbon prevents the excessive diffusivity of B and leads to a lattice-parameter reduction of 0.7–1.0%. Received: 10 January 2002 / Accepted: 30 May 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. Fax: +34-91/3974895; E-mail: Lucia.Barbadillo@uam.es     

Cavity-enhanced absorption spectroscopy with a rapidly swept diode laser

Cavity-enhanced absorption spectroscopy is explained in terms of the transmission function of a rapidly swept interferometer, and the integrated transmission is shown to be proportional to the cavity ringdown time. The technique is demonstrated on the b¹Σ_g ⁺-X³Σ_g ^-  (1,0) band in molecular oxygen at 687 nm using a tunable diode laser and a relative-ly high-Q optical cavity (finesse ≈4000). A detection limit of 3×10^-8 cm^-1 s^1/2 is achieved for a 0.8 cm^-1 scanning range. Received: 24 June 2002 / Revised version: 5 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: peverall@physchem.ox.ac.uk     

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     

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     

Tailored ablation processing of advanced biomedical hydroxyapatite by femtosecond laser pulses

The micromachining of hydroxyapatite (HAp) is highly important for orthopedics and dentistry, since human bone and teeth consist mainly of HAp. We demonstrate ultrashort Ti:sapphire laser ablation of HAp, using pulse-widths of 50 fs, 500 fs, and 2 ps at a wavelength of 820 nm and at 1 kpps. The crucial medical issue is to preserve the chemical properties of the machined (ablated) surface. If the chemical properties of HAp change, the human bone or tooth cannot re-grow after laser processing. Using X-ray photoelectron spectroscopy, we observe chemical properties of HAp ablated in air. The HAp is ablated at laser fluences of 3.2 J/cm² (6.4×10¹³ W/cm² at 50 fs), 3.3 J/cm² (6.6×10¹² W/cm² at 500 fs), and 9.6 J/cm² (4.8×10¹² W/cm² at 2 ps), respectively. As a result it is found that the ablated surface is unchanged after laser ablation over the pulse-width range used in this experiment. Received: 7 October 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +81-45/566-1533, E-mail: obara@obara.elec.keio.ac.jp     

Property study of Si + -ion-implanted Nd:YVO 4 waveguides

Planar waveguides were formed in Nd:YVO₄ crystals by 3.0-MeV Si⁺-ion implantation at doses of 1×10¹³–1.5×10¹⁵ ions/cm² at room temperature. The effective refractive indices of the waveguide propagation modes were measured by using a prism-coupling method. It was found that the number of the propagation modes is dependent on the doses for the waveguides in Nd:YVO₄. The atom displacement in the near-surface region (about 2 μm beneath the surface) of the Nd:YVO₄ crystal induced by the implantation was simulated by using the TRIM 98 (transport and range of ions in matter) code. The possible reasons for the waveguide formation are discussed in a primary way. Received: 17 July 2002 / Revised version: 20 September 2002 / Published online: 11 December 2002 RID="*" ID="*"Corresponding author. Fax: +86-531-8565167, E-mail: drfchen@sdu.edu.cn     

Structural and electrical properties of Au/Pt/Ti ohmic contacts to degenerated doped n-GaAs

The ohmic contact characteristics of Au/Pt/Ti on degenerated doped n-GaAs were evaluated. Structural and electrical properties were studied by means of X-ray diffraction (XRD), Auger Energy Spectrum (AES) and a HP4145B parameter analyzer. The structural analysis revealed a TiAs phase in the interface between metal multilayer and GaAs at higher annealing temperatures. Electrical measurement showed a minimum ohmic contact resistance of 3×10^-4 Ω cm². The dominant current mechanism was found to be thermionic emission with a barrier height of Φ_b, of 0.09 V by comparing the experimental data with different theoretical models. Received: 14 December 2001 / Accepted: 4 April 2002 / Published online: 22 November 2002 RID="*" ID="*"Corresponding author. Fax: +86-21/6226-4397, E-mail: zhoujian999@163.net     

A study of OH radicals in an atmospheric AC discharge plasma using near infrared diode laser cavity ringdown spectroscopy combined with optical emission spectroscopy

Simultaneous measurements of absolute concentrations of H₂O and OH radicals in an atmospheric AC discharge using continuous wave cavity ringdown spectroscopy (cw-CRDS) are reported. Formation of OH radicals and plasma temperatures are characterized by optical emission spectroscopy. The concentration of OH radical at the edge of the discharge plume at 380 K is measured by the cw-CRDS technique to be 1.1 ×10¹⁵ molecule cm^-3. Ringdown measurements of the H₂O (120-000) band and the OH first overtone around 1515 nm enable us to determine an OH generation yield, , to be 4.8 ×10^-3, where N_OH and are the number densities of OH and H₂O, respectively. The minimum detectable absorption coefficient of the cw-CRDS system is 8.9 ×10^-9  cm^-1, which corresponds to a 1σ detection limit of OH number density of 1.2 ×10¹³ molecule cm^-3 in the discharge. This experimental approach is demonstrated for the first time ever in an AC discharge, and can be applied in general to a variety of atmospheric plasmas to help study OH formation mechanisms and OH-related plasma applications.     

Recrystallization behavior of high-dose Mn+-implanted GaAs

Raman spectroscopy was used to study the evolution of host lattice recrystallization in Mn⁺-implanted GaAs. A high dose of Mn⁺-ions (>10¹⁵ cm^-2) was introduced into semi-insulating GaAs by the combinatorial implantation method. Subsequent thermal annealing at 920 °C was carried out to re-grow the implantation-induced amorphous layers. The dependence of the recrystallization behavior on the Mn content was systematically observed. The lattice orientation of recrystallized layers in the surface changed after high-dose implantation (>1.6×10¹⁵ cm^-2) and annealing. The size of the recrystallized crystallites decreased with increasing Mn⁺ dose, as indicated by images from atomic force microscopy. The decrease in the phonon frequency of the Raman lines with the size reduction of microcrystals was in good agreement with the spatial correlation model. However, at higher doses (>7×10¹⁶ cm^-2), a blue shift of the frequency was observed due to the compressive stress exerted on the microcrystals. Received: 5 March 2002 / Accepted: 29 August 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +86-21/658-30734, E-mail: jqwang@mail.sitp.ac.cn     

V:YAG – a new passive Q-switch for diode-pumped solid-state lasers

gsa =3.0×10^-18 cm² and σ_esa=1.4×10^-19 cm² at 1064 nm, and σ_gsa=7.2×10^-18 cm² and σ_esa=7.4×10^-19 cm² at 1342 nm. Q-switched operation was demonstrated at 1064 nm and 1342 nm from a Nd:YVO₄ microchip laser, producing pulses as short as 9.3 ns at 1342 nm with peak powers of 350 W. Received: 17 March 1998/Revised version: 8 June 1998     

Effect of the humidity on the uptake of NO<Subscript>3</Subscript> on coatings composed of MgCl<Subscript>2</Subscript> · 6H<Subscript>2</Subscript>O and MgBr<Subscript>2</Subscript> · 6H<Subscript>2</Subscript>O and mixtures thereof with NaCl

The reactive uptake of NO₃ radicals on the surface of wetted individual X salts and of wetted X-NaCl salts (X = MgCl₂ · 6H₂O and MgBr₂ · 6H₂O) at [H₂O] = 2 × 10¹²−2 × 10¹⁵ cm⁻³ and NO₃ (4.8 × 10¹² cm⁻³) was studied using a reactor with a movable insert covered with a salt coating in combination with a mass spectrometer for monitoring the initial reactant and products. The probabilities of NO₃ uptake γ on X-NaCl binary salts as functions of the content of doping salt were determined. A parametric approximation of the experimental data was proposed, which makes it possible to quantitatively predict the extent of surface enrichment of a wetted binary salt coating in doping salt and its dependence on the humidity and the content of this salt in the binary mixture. It was established that the relative surface density σ_X of X doping salt depends on its mole fraction μ_X in the X-NaCl binary salt as σ_X = aμ_X (a = 2.2 for MgBr₂ and 13.1 for MgCl₂) over the entire humidity range covered. The contributions of the X salts to the overall uptake of NO₃ at NO₃ concentration typical of the tropospheric conditions ([NO₃] ∼ 10⁷ cm⁻³ and relative humidities of RH ≤ 20%) were estimated.     

A fast-response near-infrared tunable diode laser absorption spectrometer for in situ measurements of CH4 in the upper troposphere and lower stratosphere

We describe a near-infrared in situ tunable diode laser spectrometer developed for atmospheric measurements of CH₄ in the upper troposphere and lower stratosphere (UT/LS). The instrument is designed to provide fast-response (0.5–1 Hz) measurements and operate autonomously on the NASA WB-57F high-altitude aircraft. A single-mode InGaAsP distributed feedback laser diode operating at 1.6537 μm scans continuously over the R(3) rotation–vibration transition in the 2ν₃ band. We use a direct absorption technique incorporating a custom-designed long path length (252 m) low-volume (3.6 L) astigmatic Herriott cell. The present detection sensitivity is 5×10¹⁰ molecules cm^-3, corresponding to ∼20 ppbv in the UT/LS, with the main limit to instrument precision being background optical interference fringes. In-flight performance is demonstrated by presentation of recent data. Received: 25 January 2002 / Revised version: 5 April 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-303/497-5373, E-mail: richard@al.noaa.gov     

Plasma-based nitrogen tail pulse shutter for CO2-TEA lidar dial systems

This paper presents the construction, use and characterisation of a laser-induced sealed plasma shutter to clip off the nitrogen pulse tail of a CO₂-TEA laser-based lidar dial system. Investigation of the optimum gas filling pressure, temporal profile of the clipped pulse, and the laser threshold power intensities to achieve ionisation growth and breakdown in helium, argon, and nitrogen are also presented. Values of these power density thresholds lie between 3×10¹¹ W cm^-2–5×10¹² W cm^-2, 2×10¹¹ W cm^-2–2×10¹² W cm^-2 and 3×10¹³ W cm^-2–2×10¹⁴ W cm^-2 for helium, argon, and nitrogen, respectively. The range resolution attainable with the present clipped pulses is 15 m, which is 30 times better than that readily obtained with the nitrogen-tailed pulses. Field measurements of the lidar returns with the clipped pulse from a co-operative target are presented. Received: 27 December 1999 / Revised version: 11 February 2000 / Published online: 27 April 2000