Intracavity Cr4+ :YAG laser absorption analyzed by time-resolved Fourier transform spectroscopy

A high-resolution time-resolved Fourier transform interferometer is combined with a multimode Cr⁴⁺:YAG laser for intracavity laser absorption spectroscopy (ICLAS) experiments. Atmospheric absorption spectra are recorded in the 1.5 μm region with a minimum detectable absorption coefficient equal to 8×10^-11 cm^-1 Hz^-1/2. The broad gain bandwidth of the crystal allows a simultaneous spectral coverage at most equal to 38 nm. The laser tunability covers the 1360–1577 nm range. Water vapor detection domain extends from the 100 ppmv down to the 0.1 ppbv level. PACS 42.62.Fi; 39.30.+w; 07.60.Ly; 33.20.Ea     

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     

Mid-infrared laser absorption spectrometers based upon all-diode laser difference frequency generation and a room temperature quantum cascade laser for the detection of CO, N2O and NO

We describe the performance of two mid-infrared laser spectrometers for carbon monoxide, nitrous oxide and nitric oxide detection. The first spectrometer for CO and N₂O detection around 2203 cm^-1 is based upon all-diode laser difference frequency generation (DFG) in a quasi-phase matched periodically-poled lithium niobate (PPLN) crystal using two continuous-wave room-temperature distributed feedback diode lasers at 859 and 1059 nm. We also report on the performance of a mid-infrared spectrometer for NO detection at ∼ 1900 cm^-1 based upon a thermoelectrically-cooled continuous-wave distributed feedback quantum cascade laser (QCL). Both spectrometers had a single-pass optical cell and a thermoelectrically cooled HgCdZnTe photovoltaic detector. Typical minimum detection limits of 2.8 ppmv for CO, 0.6 ppmv for N₂O and 2.7 ppmv for NO have been demonstrated for a 100 averaged spectra acquired within 1.25 s and a cell base length of 21 cm at ∼ 100 Torr. Noise-equivalent absorptions of 10^-5 and 10^-4 Hz^-1/2 are typically demonstrated for the QCL and the DFG based spectrometers, respectively. PACS  42.55.Px; 42.62.Fi; 42.65.-k; 42.72.Ai; 42.68.Ca     

Absolute, high resolution water transpiration rate measurements on single plant leaves via tunable diode laser absorption spectroscopy (TDLAS) at 1.37 μm

A new sampling-free and calibration-free multi-channel hygrometer using near infrared (NIR) tunable diode laser absorption spectroscopy (TDLAS) at 1.37 μm was developed and used to determine absolute transpiration rates of single plant leafs. Four 8×6× 4 cm³, fiber-coupled absorption cells are used to simultaneously measure absolute water vapor concentrations with an absolute accuracy of about 5% and a temporal resolution of about 2 s. Two chambers (BOTTOM, TOP) are directly attached to the leaf surface, while two chambers (IN, OUT) analyze the purge gas supplied to the plant leaf and the total outflow of the leaf chambers. The BOTTOM–TOP comparison provided a direct, leaf-side resolved ratio of stomatal conductance and–by taking into account the purge gas flow and the leaf area exposed–leaf side resolved water transpiration rates. The OUT–IN-difference yielded the total leaf transpiration rate with 2 μmol/m²/s resolution. The new multi-point hygrometer was validated by monitoring of the transpiration dynamics of a plant of the species Epipremnum pinnatum (L.) Engl. during diurnal variation of the leaf irradiation. During these experiments the differential H₂O concentration resolution between two chambers was determined to be better than 3 ppm at Δt= 2 s (i.e. better than 711 ppb m Hz^1/2). This performance was verified by an Allan analysis over a 30 min time period using CH₄ as a surrogate absorber and yielded an average optimum optical resolution of 4.9×10^-6 for 83 s measurement time, i.e. a CH₄ resolution of 892 ppb, which corresponds to the optical resolution needed for a water sensitivity of 454 ppb m Hz^1/2. PACS  07.57.Ty; 42.62.Fi; 42.62.Be; 42.55.Px; 82.80.Gk     

Difference-frequency laser spectroscopy detection of acetylene trace constituent

5 sbandpectrum. Spectroscopic detection of 28 ppmm/Hz^1/2 was performed. This corresponds to a minimum detectable mixing ratio of ∼1 ppb in conjunction with a 100-m White cell and balanced detection. Received: 3 April 1998/Revised version: 5 June 1998     

Resonance photoacoustic spectroscopy and gas analysis of gaseous flow at reduced pressure

The results of theoretical and experimental studies of sensitivity of a resonant photoacoustic Helmholtz resonator detector for gas flowing through a photoacoustic cell under reduced pressure are presented. The measurements of the sensitivity and ultimate sensitivity of the differential photoacoustic cell were performed with a near-IR room-temperature diode laser using the well-known H₂O absorption line (12496.1056 cm^-1) as a reference. The measured value of the sensitivity (6–17 Pa W m^-1) is in satisfactory agreement with the calculated one, which equals 6–35 Pa W m^-1. The obtained value of the ultimate sensitivity ((3–5)×10^-7 W m^-1 Hz^-1/2) provides measurements of the concentration of molecules at the ppb–ppm level. Received: 19 April 2001 / Revised version: 18 September 2001 / Published online: 7 November 2001     

A water isotope (2H, 17O, and 18O) spectrometer based on optical feedback cavity-enhanced absorption for in situ airborne applications

Measurements of the isotopic composition of water are thought to help explain stratospheric aridity and related issues in atmospheric sciences. Simultaneous in situ measurements of ²H/¹H, ¹⁷O/¹⁶O, and ¹⁸O/¹⁶O at high spatial resolution are required for this purpose. We present the design and laboratory performance of a device that will be used on high-altitude research aircraft. It is based on optical feedback cavity-enhanced spectroscopy (OF-CEAS), with better sensitivity than traditional multi-pass arrangements. It utilizes a near-infrared laser source, avoiding the need for cryogens. We demonstrate an airborne precision during tropospheric flight conditions of 1 ‰, 3 ‰, and 9 ‰ for δ¹⁸O, δ¹⁷O, and δ²H, respectively, for 30-s averaged data and a water concentration of about 200 ppm. With recent improvements we expect to remain within a factor of about three of these values under true stratospheric conditions (water mixing ratio ∼10 ppmv). PACS 07.88.+y; 42.55.Px; 42.62.Fi; 92.60.Hd; 92.60.Jq     

A sensitivity comparison of three photoacoustic cells containing a single microphone,a differential dual microphone or a cantilever pressure sensor

Three photoacoustic (PA) cells designed for trace-gas sensing were compared by measuring absorption by the P(15) rotational line of the vibrational combination band of acetylene using a distributed-feedback diode laser. Normalised sensitivities were determined for each cell by analysis of the signal to noise ratios of acquired spectra. The first cell was constructed in-house, and contained a single electret microphone held in a stainless steel tube. The second cell was a differential PA cell that contained two microphones housed in identical flow tubes, with one microphone to detect the PA signal and the other to determine background noise levels. The third cell contained a novel cantilever pressure sensor, movement of which was measured by a compact laser interferometer. Normalised sensitivities (2σ) of 3.1×10^-7, 1.7×10^-7 and 2.2×10^-9 cm^-1 W Hz^-1/2, respectively, were obtained. An erbium-doped fibre amplifier was used to amplify the laser power, and a detection limit of 9.8×10¹⁰ molecule cm^-3 was obtained using the cantilever pressure sensor PA cell, with a laser power of 1.17 W. This detection limit corresponded to a mixing ratio of 14.5 parts per billion by volume at 277 mbar. PACS 82.80.Kq; 42.62.Fi; 82.80.Gk     

High resolution ethylene absorption spectrum between 6035 and 6210 cm-1

A two-channel photo-acoustic spectrometer (PA spectrometer) with a near infrared diode laser was used for taking measurements of a high resolution ethylene absorption spectrum. A semiconductor TEC-100 laser with an outer resonator generates a continuous single-frequency radiation in the range 6030–6300 cm^-1. A newly designed model of photo-acoustic detector (PAD) in the form of a ring type resonator provides for measurement of weak absorption cross-section equal to 4×10^-23 cm²/mol at a laser radiation power of 3 mW. The PAD threshold sensitivity is 2×10^-9 cm^-1 Hz^-1/2 W, when the signal to noise ratio equals to 1. The ethylene absorption spectrum within the range 6035–6210 cm^-1 was measured for the first time with a spectral resolution of 10 MHz. The reported line centre positions have an uncertainty of ± 0.0005 cm^-1. The precise measurements of ethylene absorption cross-sections were carried out using the mixture of high purity ethylene and broadening gas (nitrogen) at the mixture ratio 1:50–1:200. Measurements were carried out at a mixture pressure of about 4.2 kPa. PACS 42.62.Fi; 42.55.Px     

Continuous wave optical parametric oscillator for quartz-enhanced photoacoustic trace gas sensing

A continuous wave optical parametric oscillator, generating up to 300 mW idler output in the 3–4 μm wavelength region, and pumped by a fiber-amplified DBR diode laser is used for trace gas detection by means of quartz-enhanced photoacoustic spectroscopy (QEPAS). Mode-hop-free tuning of the OPO output over 5.2 cm^-1 and continuous spectral coverage exceeding 16.5 cm^-1 were achieved via electronic pump source tuning alone. Online monitoring of the idler wavelength, with feedback to the DBR diode laser, provided an automated closed-loop control allowing arbitrary idler wavelength selection within the pump tuning range and locking of the idler wavelength with a stability of 1.7×10^-3 cm^-1 over at least 30 min. Using this approach, we locked the idler wavelength at an ethane absorption peak and obtained QEPAS data to verify the linear response of the QEPAS signal at different ethane concentrations (100 ppbv-20 ppmv) and different power levels. The detection limit for ethane was determined to be 13 ppbv (20 s averaging), corresponding to a normalized noise equivalent absorption coefficient of 4.4×10^-7 cm^-1  W/Hz^1/2. PACS 42.55.Wd; 42.65.Yj; 42.62.Fi     

Two-tone frequency modulation spectroscopy for ambient-air trace gas detection using a portable difference-frequency source around 3 μm

We report a portable, widely tunable, mW-power mid-infrared spectrometer based on difference-frequency generation in a periodically poled lithium-niobate crystal, realized in a compact and robust design. The analytical performance for real-time monitoring of natural-abundance trace gases in ambient air is evaluated, pointing out the possibility of field applications. In a direct-absorption scheme, a minimum detectable concentration of 3 ppb Hz^-1/2 is demonstrated around 3.3 μm for methane at atmospheric pressure. The sensitivity is further improved by using a two-tone frequency modulation spectroscopy technique that provides an enhancement of a factor of 100 in the signal-to-noise ratio, thus yielding a minimum absorption coefficient of 5.3×10^-9 cm^-1 Hz^-1/2. PACS 42.72.Ai; 42.81.Wg; 42.68.Ca     

Wavelength modulated off-axis integrated cavity output spectroscopy in the near infrared

A novel instrument based on an improved off-axis alignment of integrated cavity output spectroscopy (OA-ICOS) in conjunction with a wavelength modulation (WM) technique, was developed using a DFB diode laser operating in the near infrared at 1.573 μm (6357.3 cm^-1). The laser-based sensor employed a 44 cm optical cavity that provided an effective absorption path length of ∼68 m. A minimum detectable absorption of approximately 3.6 ppmv Hz^-1/2 or 2.3×10^-7 Hz^-1/2 per optical pass was obtained using second harmonic detection. We demonstrated that by implementation of the WM technique to OA-ICOS in the near infrared, the detection sensitivity was improved by a factor of 14 compared to that obtained with OA-ICOS. Measurements of CO₂ mixing ratios in ambient air have been performed by using both OA-ICOS and WM-OA-ICOS techniques for performance comparison. PACS 42.62.Fi; 07.07.Df; 33.20.Ea     

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     

Wireless laser spectroscopic sensor node for atmospheric CO2 monitoring—laboratory and field test

We developed a low-power, portable, wireless laser spectroscopic sensor for atmospheric CO₂ monitoring. The sensor is based on tunable diode laser absorption spectroscopy with a 2-μm wavelength VCSEL as a source and wavelength modulation technique for spectroscopic signal detection. The sensor allows measurement of CO₂ concentration changes with a 1σ sensitivity of 0.14 ppmv?Hz^?1/2. This sensor was both laboratory and field tested under varying environmental conditions. It was used to measure a soil respiration rate of topsoil in the lab and of forest floors in the field. Measurement results are compared with those of commercial non-dispersive infrared sensors and very good agreement is found.     

Photoacoustic detection of oxygen using cantilever enhanced technique

A tunable diode laser photoacoustic setup based on a recently demonstrated cantilever technique was used for sensitive detection of oxygen. As light sources, we used a distributed feedback (DFB) diode laser and a vertical-cavity surface-emitting (VCSEL) laser, both operating near 760 nm. With the 30 mW DFB laser a noise-equivalent detection limit of 20 ppm for oxygen was obtained, while a detection limit of 5 ‰ was achieved with the VCSEL having an output power of 0.5 mW. Our results yield a noise-equivalent sensitivity of 4.8×10^-9 cm^-1W Hz^-1/2 and demonstrate the potential of this technique for compact and sensitive measurement of oxygen. PACS 42.62.Fi; 42.55.Px; 82.80.Kq     

An off-axis cavity-enhanced absorption spectrometer at 1605 nm for the 12CO2/13CO2 measurement

A distributed feedback diode laser sensor based upon off-axis cavity-enhanced absorption spectroscopy at 1605.5 nm has been developed for ¹³C¹⁶O₂/¹²C¹⁶O₂ isotope ratio measurements in synthetic air and human breath. A noise-equivalent absorption sensitivity of 3.9×10^-10 cm^-1 Hz^-1/2 has been determined for a cavity base length of 28.2 cm and averaging 4000 scans within 8.688 s. For 5% CO₂ concentration measurements, δ¹³C standard deviations of 1.8 ‰ and 3.7 ‰ have been estimated for five successive measurements based on peak height and integrated area estimations at 107.9 Torr, respectively. The contributions of amplified spontaneous emission of the laser and a radiation that is spatially uncoupled into the cavity mode have been described for cavity transmittance measurements. The limitations of the developed sensor and further steps towards precision and accuracy improvements are discussed. PACS 42.55.Px; 39.30.+w; 42.62.Fi; 42.60.-v     

Collective behavior of laser-produced plasma from a multicomponent YBa2Cu3O7 target in air

2 Cu₃O₇, using a Q-switched Nd:YAG laser is investigated by time-resolved emission-spectroscopic techniques at various laser irradiances. It is observed that beyond a laser irradiance of 2.6×10¹¹ W cm^-2, the ejected plume collectively drifts away from the target with a sharp increase in velocity to 1.25×10⁶ cm s^-1, which is twice its velocity observed at lower laser irradiances. This sudden drift apparently occurs as a result of the formation of a charged double layer at the external plume boundary. This diffusion is collective, that is, the electrons and ions inside the plume diffuse together simultaneously and hence it is similar to the ambipolar diffusion of charged particles in a discharge plasma. Received: 30 January 1998/Revised version: 12 June 1998     

Laser-induced fluorescence study of a xenon Hall thruster

2 ⁰→6p[3/2]₂(³P₂-¹D₂) transition at 823.2 nm and the xenon-ion 5d[3]_7/2→6p[2]_5/2 ⁰(⁴D_7/2-⁴P_5/2) transition is used to measure plasma parameters in the plume of a laboratory-model xenon Hall thruster. The Hall discharge operates nominally at 62 V, 4.2 A, and 3.2 mg s^-1 xenon flow, with an overall thruster power of 320 W. A tunable semiconductor diode laser and an Ar⁺-pumped dye laser are used to probe the respective excited-state transitions. Axial velocity measurements are made at a number of axial and radial locations up to 4.5 cm downstream of the thruster-exit plane and under a variety of thruster operating conditions. Neutral velocities from 100 m s^-1 to 400 m s^-1 and ion velocities as high as 12 km s^-1 are calculated from measured Doppler shifts. The charge-exchange phenomenon evidently does not significantly affect the xenon neutrals. The spectral-line shapes of the ion indicate a spread in ion energies through a non-Maxwellian distribution of axial velocities. Neutral kinetic temperatures of 500 (±200) K are observed under standard operating conditions. Zeeman and Stark effects on the spectral-line shapes, from the thruster’s magnetic and electric fields, are not substantial. The measured line center of the ion transition is 16521.23 (±0.02) cm^-1. Received: 20 January 1997/Revised version: 12 May 1997     

Cantilever-based photoacoustic detection of carbon dioxide using a fiber-amplified diode laser

A compact and sensitive photoacoustic setup has been developed based on a recently demonstrated cantilever technique. A micromechanical cantilever transducer is attached to a cylindrical photoacoustic cell and the cantilever’s deflection is monitored with a compact Michelson interferometer. A commercial 1-Watt optical fiber amplifier was used to enhance the performance of the system. A normalized sensitivity of 1.4×10^-10 cm^-1 W Hz^-1/2 was achieved in the detection of carbon dioxide at 1572 nm wavelength. Using 34 mW optical power from a DFB diode laser, the noise-equivalent detection limit for carbon dioxide at this wavelength is 4.0 ppm. Employing the fiber amplifier, we improved the sensitivity to yield measurement of sub-ppm concentrations. PACS 42.62.Fi; 42.55.Px; 82.80.Ch