Photoacoustic measurement of N2O concentrations in ambient air with a pulsed optical parametric oscillator

Photoacoustic spectroscopy, in combination with a pulsed grazing-incidence optical parametric oscillator (GIOPO), was used for sensitive detection of nitrous oxide (N₂O) in ambient air. The ν₁+ν₃ combination band of N₂O was excited with the idler beam of the GIOPO in the 2.76 μm–2.91 μm spectral region, where CO₂ and water-absorption lines are also present. Three chemical filters filled with KOH, CaCl₂, and P₂O₅ were used to reduce the CO₂ and water concentrations to the level of several parts per billion (10⁹) by volume (ppbv). Photoacoustic spectra containing several absorption lines were recorded and the concentration was determined by an integral evaluation method and a fast Fourier transform evaluation method. The photoacoustic signal was calibrated by a standard mixture of 50.6 parts per million by volume (ppmv) of N₂O in synthetic air. Values of 311±5 ppbv, 314±5 ppbv, and 316±5 ppbv were found for three ambient samples collected at nearby roads. PACS 42.62.Fi; 42.65.Yj; 07.07.Df; 42.68.Ca     

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     

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     

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     

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     

Rapidly swept, continuous-wave cavity ringdown spectroscopy with optical heterodyne detection: single- and multi-wavelength sensing of gases

Spectroscopic sensing of gases can be performed with high sensitivity and photometric precision by cavity ringdown (CRD) absorption spectroscopy. Our cavity ringdown spectrometer incorporates continuous-wave (cw) tunable diode lasers, fibre-optic coupling and standard photonics and optical telecommunications components. It comprises a rapidly swept optical cavity in a single-ended optical heterodyne transmitter–receiver configuration, enabling optical absorption of gases to be recorded either as single-frequency scanned spectra or as simultaneous, multi-wavelength tailored spectra. By measuring weak near-infrared rovibrational spectra of carbon dioxide gas (CO₂), with high resolution in the vicinity of 1.53 μm, we have realised a noise-limited absorption sensitivity of 2.5×10^-9 cm^-1 Hz^-1/2. Analytical sensitivity limits (both actual and projected) and prospective gas-diagnostic applications are discussed. Our approach to cw-CRD spectroscopy offers high performance in a relatively simple, low-cost, compact instrument that is amenable to chemical analysis of trace gases in medical, agricultural, industrial and environmental situations. Received: 16 May 2002 / Revised version: 3 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +61-2/9850-8313, E-mail: brian.orr@mq.edu.au     

Compact diode-side-pumped Nd:YVO<Subscript>4</Subscript> laser in grazing-incidence configuration

The analysis of compact CW diode-side-pumped grazing-incidence-geometry Nd:YVO₄ laser designs is presented. An output power of 5 W (λ=1064 nm) was produced at 17 W of diode pump (conversion efficiency of 30%) in single transverse TEM₀₀ mode operation at high laser beam quality (M_x ²≈1.05 and M_y ²≈1.01). The resonator geometry was analyzed by applying generalized 4×4 matrix modeling of the spatial mode size, including the impact on the laser operation of cavity astigmatism and a thermal lens in the laser slab. The simplicity and compactness of the laser cavities allow their use for technological applications. Received: 31 July 2002 / Published online: 22 January 2003 RID="*" ID="*"Corresponding author. Fax: +44-20/7594-7744, E-mail: m.damzen@ic.ac.uk     

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     

In situ observation of dynamics of plasma self-channeling and bulk modification in silica glasses induced by a high-intensity femtosecond laser

The time-resolved dynamics of plasma self-channeling and refractive index bulk modification in silica glasses were first observed in situ using a high-intensity femtosecond (110 fs) Ti:sapphire laser (λ_p=790 nm). Plasma channeling is induced in silica glass at an irradiation higher than an input intensity of 1.5×10¹² W/cm² and photoinduces either the refractive-index modification or optical crack modification. In the domain of refractive-index modification, the lifetime of induced plasma self-channeling was 20 ps and the structural transition time for forming the refractive-index change was 10 ps. In the domain of optical cracks, however, the lifetime of induced plasma formation was 30 ps and the structural transition time for forming the optical cracks was 40 ps. According to electron spin resonance spectroscopic (ESP) measurement, it was found that the defect concentration of the SiE^′ center increased significantly in the refractive index modification region. A maximum value of the refractive-index change Δn was measured to be 1.6×10^-2. The intensity profile of the output beam transmitted through the refractive-index modification showed that the bulk modification produced a permanent optical waveguide. Received: 8 April 2002 / Accepted: 12 April 2002 / Published online: 22 November 2002 RID="*" ID="*"Corresponding author. Fax: +81-48/462-4682, E-mail: shcho@riken.go.jp     

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     

Ultra-sensitive mid-infrared cavity leak-out spectroscopy using a cw optical parametric oscillator

We report a portable, all-solid-state, mid-infrared spectrometer for trace-gas analysis. The light source is a continuous-wave optical parametric oscillator based on PPLN and pumped by a Nd:YAG laser at 1064 nm. The generated single-frequency idler output covers the wavelength region between 2.35 and 3.75 μm. With its narrow line width, this light source is suitable for precise trace-gas analysis with very high sensitivity. Using cavity leak-out spectroscopy we achieved a minimum detectable absorption coefficient of 1.2×10^-9 /cm (integration time: 16 s), corresponding, for example, to a detection limit of 300 parts per trillion ethane. This sensitivity and the compact design make this trace-gas analyzer a promising tool for various in situ environmental and medical applications. Received: 19 September 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +49-228/733-474, E-mail: frank.kuehnemann@iap.uni-bonn.de     

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     

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     

Cavity ring-down spectroscopy for atmospheric trace gas detection: application to the nitrate radical (NO3)

Cavity ring-down spectroscopy is a relatively new and quite sensitive technique for the measurement of gas-phase optical extinction. It holds the potential for simple, direct and sensitive measurement of the concentrations of a variety of trace gases in the atmosphere. For example, detection of the nitrate radical, NO₃, and its companion, dinitrogen pentoxide, N₂O₅, has been demonstrated with a sensitivity of 0.25 pptv (1σ). This paper considers several of the requirements for the application of cavity ring-down spectroscopy to concentration measurements of trace gases in ambient air. These include detection sensitivity, measurement of an accurate zero in the presence of competing absorbers, cavity stability and mirror cleanliness, laser line-width effects, saturation effects, Rayleigh scattering, the influence of atmospheric aerosols and sampling issues for reactive species. Examples drawn from our work on NO₃ and N₂O₅ detection in the field illustrate these considerations. Received: 1 April 2002 / Revised version: 5 June 2002 / Published online: 12 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-303/497-5822, E-mail: sbrown@al.noaa.gov     

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     

Mid-infrared polarization spectroscopy of carbon dioxide

The use of mid-infrared polarization spectroscopy (PS) for the detection of CO₂ has been demonstrated. The P(13) and P(14) resonances of the (0 0⁰ 0)→(1 0⁰ 1) transition of CO₂ were probed using a single-mode optical parametric generator system to produce a high-intensity laser beam at approximately 2.7 μm. The experiments were performed in an atmospheric pressure CO₂ jet and also in a sub-atmospheric pressure gas cell. The experimental results were compared with the results of the time-dependent density-matrix equations using direct numerical integration. The Zeeman-state structure of the upper and lower energy levels was included in the multi-state formulation of the density-matrix equations. Fifty-eight Zeeman states and two bath levels were included in the numerical analysis of the P(14) transition. The measured and calculated PS line shapes were in good agreement, and the absolute experimental signal level agreed with the theoretical calculation to within a factor of five. Received: 20 March 2002 / Revised version: 16 August 2002 / Published online: 11 December 2002 RID="*" ID="*"Present address: Innovative Scientific Solutions Inc., 2766 Indian Ripple Road, Dayton, OH 45 440, USA RID="**" ID="**"Corresponding author. Fax: +1-765/494-0539, E-mail: Lucht@purdue.edu RID="***" ID="***"Present address: School of Mechanical Engineering, Purdue University, W. Lafayette, IN 47807-2040 USA     

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     

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     

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     

Coherent coupling of a single <Superscript>40</Superscript>Ca<Superscript>+</Superscript> ion to a high-finesse optical cavity

We demonstrate coherent coupling of the quadrupole S_1/2D_5/2 optical transition of a single trapped ⁴⁰Ca⁺ ion to the standing wave field of a high-finesse cavity. The dependence of the coupling on temporal dynamics and spatial variations of the intracavity field is investigated in detail. By precisely controlling the position of the ion in the cavity standing wave field and by selectively exciting vibrational state-changing transitions the ion’s quantized vibration in the trap is deterministically coupled to the cavity mode. We confirm coherent interaction of ion and cavity field by exciting Rabi oscillations with short resonant laser pulses injected into the cavity, which is frequency-stabilized to the atomic transition. Received: 23 August 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. E-mail: christoph.becher@uibk.ac.at RID="**" ID="**"Present address: Time and Frequency Division, National Institute of Standards and Technology, Boulder, CO 80305, USA