Application of InAsSb/InAsSbP and lead chalcogenide infrared diode lasers for photoacoustic detection in the 3.2 and 5 microm region

An investigation of photoacoustic detection using 3.2-3.6 and 5 mum diode lasers is described. An inexpensive resonant photoacoustic system was developed based, on a simple glass cell and condenser and electret microphone (Brüel & Kjaer type 4144/Sennheiser type K6P). The system was tested on the single rotation-vibration lines of C(2)H(2), CO, COS, and NH(3) gases. The best detection limits obtained are 300 ppm V for C(2)H(2) and 20 ppm V for COS. Potential applications of infrared diode laser photoacoustic detection lie in the areas of analytical chemistry, atmospheric research, and investigation of the kinetics of reactive species.     

Novel Helmholtz-based photoacoustic sensor for trace gas detection at ppm level using GaInAsSb/GaAlAsSb DFB lasers

A new and compact photoacoustic sensor for trace gas detection in the 2-2.5 microm atmospheric window is reported. Both the development of antimonide-based DFB lasers with singlemode emission in this spectral range and a novel design of photoacoustic cell adapted to the characteristics of these lasers are discussed. The laser fabrication was made in two steps. The structure was firstly grown by molecular beam epitaxy then a metallic DFB grating was processed. The photoacoustic cell is based on a Helmholtz resonator that was designed in order to fully benefit from the highly divergent emission of the antimonide laser. An optimized modulation scheme based on wavelength modulation of the laser source combined with second harmonic detection has been implemented for efficient suppression of wall noise. Using a 2211 nm laser, sub-ppm detection limit has been demonstrated for ammonia.     

Tunable fiber laser and fiber amplifier based photoacoustic spectrometer for trace gas detection

A new wavelength modulated photoacoustic spectrometer based on a near-infrared tunable erbium doped fiber laser (TEDFL) and an erbium doped fiber amplifier (EDFA) is first developed for trace gas detection. This sensor has been applied to the detection of ammonia using a first longitudinal resonant photoacoustic cell with double absorption optical path (L = 20 cm) and lock-in harmonic detection technique. The minimum detectable limit of 3 parts-per-billion volume (signal-to-noise ratio = 1) and response time of approximately 1 min is achieved at room temperature and atmospheric pressure with 100 ms time constant and 500 mW optical power at the 1531.7 nm transition line.     

Sub-ppm multi-gas photoacoustic sensor

A photoacoustic multi-gas sensor using tuneable laser diodes in the near-infrared region is reported. An optimized resonant configuration based on an acoustic longitudinal mode is described. Automatic tracking of the acoustic resonance frequency using a piezo-electric transducer and a servo electronics is demonstrated. Water vapour, methane and hydrogen chloride have been measured at sub-ppm level in different buffer gas mixtures. The importance of the system calibration in presence of several diluting gases is discussed. Finally, trace gas measurements have been assessed and detection limits (signal-to-noise ratio=3) of 80 ppb at 1651.0 nm for CH(4), 24 ppb at 1368.6 nm for H(2)O and 30 ppb at 1737.9 for HCl have been demonstrated.     

Photoacoustic spectrometry for trace gas analysis and leak detection using different cell geometries

A photoacoustic (PA) spectrometer with high selectivity and sensitivity has been developed for trace gas analysis and for the detection of gas leak at part per trillion by volume (pptV) level. This PA system comprises of a resonant photoacoustic cell, a pulsed line tunable CO₂ laser as an excitation source and a sensitive electret microphone as a photoacoustic detector with an option to trigger the safety alarm system for early warning of gas leaks. In this work, three resonant PA cells with various geometries have been developed at our laboratory for the detection of photoacoustic signal using pulsed laser system and their comparative performance have been studied. As a special application of this PA system, the detection of sulfur hexa fluoride (SF₆) gas using these three cells has been carried out for optimizing the sensitivity. Besides this, our PA system can very well be applied for pollution monitoring and detection of hazardous gases in a noisy environment.     

Laser diode photoacoustic detection in the infrared and near infrared spectral ranges

A new technique for high resolution photoacoustic detection based on application of laser diodes has been developed. This method was tested and compared using identical photoacoustic instrumentation (cell and microphone) to study gas absorption in three different spectral regions, namely: the infrared range near 2100 cm(-1), CO and OCS fundamental band absorption; the ranges near 4200 and 4350 cm(-1), CH4, NH3 and N2O overtone and combination band absorption; the near infrared range near 6500 cm(-1), CO, CO2 and NH3 overtone absorption. Several types of diode laser operating at room temperature or at liquid nitrogen temperature were compared. The optimum gas pressures for the maximum sensitivity of the photoacoustic signals were found and the detection limits were estimated for all of the gases studied. The best sensitivity was achieved for NH3 at 100 ppbv. The sensitivity of the developed system was tested on detection of traces of NH3 and CO2 gases from car exhaust.     

Near-infrared diode laser wavelength modulation-based photoacoustic spectrometer

An inexpensive resonant photoacoustic spectrometer based on a low-power distributed feedback diode laser and wavelength modulation spectroscopy is developed. This sensor has been applied to the detection of acetylene (C2H2) using a properly designed photoacoustic cell operating on its second longitudinal mode. The minimum detectable limit of about 10 parts-per-million volume (signal to noise ratio=1) is achieved at atmospheric pressure, and the pressure and laser power linear dependence of the photoacoustic signal is also investigated. Moreover, in this paper we also describe some basic theory of gas photoacoustic spectroscopy.     

High-resolution spectra of bromo methane and methyl bromide obtained by a continuously tunable 10-bar CO2 laser based photoacoustic spectrometer.

High resolution spectral data of 100 ppmV (10(-6) per volume) concentrations of the trace gases bromo methane (BM, CH3Br), and methyl bromide (DME, (CH3)2O), buffered in synthetic air (80% N2, 20% O2) at atmospheric pressure and room temperature are reported. The spectra are recorded with a continuously tunable 10-bar CO2 laser based photoacoustic (PA) spectrometer. The tuning range covers 76 cm(-1) between 9.2 microm (1087 cm(-1)) and 10.7 microm (935 cm(-1)) at a constant narrow line-width of 0.018 cm(-1) (540 MHz). The non-resonant PA measuring cell employs an in-line 10-microphone array. The estimated detection limits for BM and DME are approximately 2 ppmV for a signal-to-noise ratio (SNR) of 3. This corresponds to a calculated detection limit of approximately 76 ppbV for ethylene.     

Detection of malathion by the CO2 laser: Potentials and limitations

Possibilities of on-line non-contact detection of the vapour of the commercially available pesticide malathion by the CO₂ laser were investigated, using a photoacoustic technique developed in our laboratory. A set of laser/vapour spectral coincidences in the usual range of CO₂ laser wavelengths were obtained, the samples being: the commercial product Etiol available on the market, solvent, emulsifiers, and neat malathion, all with air added to a mid-pressure of about 100 mbar and to atmospheric pressure. Relative contributions of the components in the product are discussed. A detection limit of 0.002 vol.% of the product in air was estimated.     

Application of copper sulfate pentahydrate as an ammonia removal reagent for the determination of trace impurities in ammonia by gas chromatography

Rapid analysis of trace permanent gas impurities in high purity ammonia gas for the microelectronics industry is described, using a gas chromatograph equipped with a phtoionization detector. Our system incorporates a reactive precolumn in combination with the analytical column to remove the ammonia matrix peak that otherwise would complicate the measurements due to baseline fluctuations and loss of analytes. The performance of 21 precolumn candidate materials was evaluated. Copper sulfate pentahydrate (CuSO₄·5H₂O) was shown to selectively react with ammonia at room temperature and atmospheric column pressures, without affecting the hydrogen, oxygen, nitrogen, methane or carbon monoxide peak areas. To prevent loss of trace carbon dioxide, an additional boron trioxide reactant layer was inserted above the copper sulfate pentahydrate bed in the reactive precolumn. Using the combined materials, calibration curves for carbon dioxide proved to be equivalent in both ammonia and helium matrix gases. These curves were equivalent in both matrix gases. The quantitative performance of the system was also evaluated. Peak repeatabilities, based on eight injections, were in the range of 4.1–8.2% relative standard deviation; and detection limits were 6.9 ppb for H₂, 1.8 ppb for O₂, 1.6 ppb for N₂, 6.4 ppb for CH₄, 13 ppb for CO, and 5.4 ppb for CO₂.     

Open path atmospheric spectroscopy using room temperature operated pulsed quantum cascade laser

We report the application of a distributed feedback quantum cascade laser for 5.8 km long open path spectroscopic monitoring of ozone, water vapor and CO(2). The thermal chirp during a 140 or 200 ns long excitation pulse is used for fast wavelength scanning. The fast wavelength scanning has the advantage of the measured spectra not being affected by atmospheric turbulence, which is essential for long open path measurements. An almost linear tuning of about 0.6 and 1.2 cm(-1) is achieved, respectively. Lines from the nu(3) vibrational band of the ozone spectra centered at 1,031 and 1,049 cm(-1) is used for ozone detection by differential absorption. The lowest column densities (LCD) for ozone of the order of 0.3 ppmm retrieved from the absorption spectra for averaging times less than 20s are better then the LCD value of 2 ppmm measured with UV DOAS systems. The intrinsic haze immunity of mid-IR laser sources is an additional important advantage of mid-IR open path spectroscopy, compared with standard UV-vis DOAS. The third major advantage of the method is the possibility to measure more inorganic and organic atmospheric species compared to the UV-vis DOAS.     

Photoacoustic study of CO2-laser coincidences with absorption of some organic solvent vapours

Detection of specific molecules in the atmosphere is motivated by the need for monitoring the emission of industrial pollutants. CO₂-laser photoacoustic (PA) spectroscopy was used here to obtain coincidence spectra of the vapours of three organic solvents: trichloroethylene (TCE), benzene, and dioxan. Spectra of coincidences were obtained as a function of total pressure, adding dry air to the vapour of the solvents up to 1000 mbar.A narrow cavity photoacoustic cell with window acoustic buffers was built for improved sensitivity, and is reported here.The vapour molecules studied do have some significant absorption in the CO₂-laser region, or close to it, but that fact does not necessarily lead to usable coincidences with the narrow laser lines. The results reveal several prominent coincidences that can be used for practical purposes, especially in the case of trichloroethylene.     

Direct Measurement of SO2 in Air by Laser Induced Fluorescence Spectrometry Using a Nontunable Laser Source

Studies have been performed to evaluate a direct laser induced fluorescence (LIF) technique for measurements of atmospheric sulfur dioxide (SO₂). The technique is novel in that it uses a nontunable laser source that is spectrally coincident with absorption of the SO₂ molecule near 223 nm that allows sensitive measurements at environmentally relevant concentrations. In this report, the spectral characteristics and analytical capabilities of the nontunable LIF approach have been evaluated and preliminary measurements of ambient SO₂ are reported. The current limit of detection is 0.5 ppb and compares well to other analytical spectroscopy methods used for atmospheric measurements of SO₂. The results indicate strong feasibility for the nontunable LIF approach for SO₂ measurements and suggest ways for method improvement.     

Sensitive Detection of Aromatic Molecules by Laser Photoacoustic Spectrometry: Signal Enhancement by Fluorescence Quencher

Highly sensitive detection of aromatic molecules has been investigated by pulsed laser excitation. A cylindrical cell surrounded by a piezoelectric transducer has improved the detection limit. Fluorescence quencher, CH₃NO, increased the photoacoustic signal of perylene up to three times and the signal-to-noise ratio by about 50%. Typical detection limits of pyrene and perylene were 0.4 ppb in hexane and 6.7 ppb in methanol with nitromethane, respectively.     

用于负压下气体分析的气相色谱仪的研制

介绍一种可同时分析负压样品中常量Ｏ２,Ｎ２,ＣＯ和微量ＣＯ２的自制专用气相色谱仪。仪器在 负压下取样,经活塞升压后进样。在流程中样品气同时进入并列的色谱柱,再分别检测。常量组分使用热导池检测,微量组分使用氦离子化检测器检测。ＣＯ２的检测灵敏度为１０＾－６量级。实验表明,仪器结构简单,操作方便稳定性好,适合于负压气样的在线分析,负压气样中全组分的分析方法具有推广价值。     

Intra-puff CO and CO2 measurements of cigarettes with iron oxide cigarette paper using quantum cascade laser spectroscopy

The objective of this research was to apply Fourier transform infrared spectroscopy (FTIR) and tunable infrared laser differential absorption spectroscopy (TILDAS) for measuring selected gaseous constituents in mainstream (MS) and sidestream (SS) smoke for experimental cigarettes designed to reduce MS CO using iron oxide cigarette papers. These two complimentary analytical techniques are well suited for providing per puff smoke deliveries and intra-puff evolution profiles in cigarette smoke respectively. The quad quantum cascade (QC) laser high resolution infrared spectroscopy system has the necessary temporal and spectral resolution and whole smoke analysis capabilities to provide detailed information for CO and CO(2) as they are being formed in both MS and SS smoke. The QC laser system has an optimal data rate of 20 Hz and a unique puffing system, with a square wave shaped puff, that allows whole smoke to enter an 18 m, 0.3 L multi-pass gas cell in real time (0.1s cell response time) requiring no syringe or Cambridge filter pad. Another similar multi-pass gas cell with a 36 m pathlength simultaneously monitors the sidestream cigarette smoke. The smoke from experimental cigarettes manufactured with two types of iron oxide papers were compared to the smoke from cigarettes manufactured similarly without iron oxide in the paper using both instrument systems. The delivery per puff determined by the QC laser method agreed with FTIR results. MS CO intra-puff evolution profiles for iron oxide prototype cigarettes demonstrated CO reduction when compared to cigarettes without iron oxide paper. Additionally, both CO and CO(2) intra-puff evolution profiles of the cigarettes with iron oxide paper showed a significant reduction at the initial portion of the 2 s puff not observed in the non-iron oxide prototype cigarettes. This effect also was observed for ammonia and ethylene, suggesting that physical parameters such as paper porosity and burn rate are important. The SS CO and CO(2) deliveries for the experimental cigarettes evaluated remained unaffected. The iron oxide paper technology remains under development and continues to be evaluated.     

Application of antimonide diode lasers in photoacoustic spectroscopy

First investigations of photoacoustic (PA) spectroscopy (PAS) of methane using an antimonide semiconductor laser are reported. The laser fabrication is made in two steps. The structure is firstly grown by molecular beam epitaxy, then a metallic distributed-feedback (DFB) grating is processed. The laser operates at 2371.6 nm in continuous wave and at room temperature. It demonstrates single-mode emission with typical tuning coefficients of 0.04 nm mA(-1) and 0.2 nm K(-1). PA detection of methane was performed by coupling this laser into a radial PA cell. A detection limit of 20 ppm has been achieved in a preliminary configuration that was not optimised for the laser characteristics.     

Graphdiyne:a Highly Sensitive Material for ppb-Level NO2 Gas Sensing at Room Temperature

Detection of a trace amount of NO2 at room temperature has very important applications in air quality monitoring,protection of human health and medical diagnose.However,the existing NO2 sensors often suffer from low sensitivity when the concentration at the ppb-level.Here,we report a new kind of materials based on graphdiyne(GDY)for highly sensitive detection of ppb-level(ppb:part per billion)NO2 at room temperature.After thermal treatment of the as-prepared GDY at 600℃under argon atmosphere for 2 h(the obtained sample denoted as GDY-600),the prepared sensor with GDY-600 displays excellent sensitivity with a response value of 6.2％towards 250 ppb NO2 at room temperature,which is better than most of reported sensing materials.In addition,the sensor exhibits significantly high selectivity to NO2 against typical interfering gases including CO,CO2,NH3,H2,H2S and toluene.Moreover,the sensor shows remarkable stability after repetitive measurements.The superior sensing performance of GDY-600 can be ascribed to the highly π-conjugated structure with special acetylenic bonds and abundant oxygen-containing functional groups,which are all beneficial for the gas adsorption and redox reaction on the surface.