Cavity ring down spectroscopy: detection of trace amounts of substance

We describe several applications of cavity ring-down spectroscopy (CRDS) for trace matter detection. NO₂ sensor was constructed in our team using this technique and blue-violet lasers (395–440 nm). Its sensitivity is better than single ppb. CRDS at 627 nm was used for detection of NO₃. Successful monitoring of N₂O in air requires high precision mid-infrared spectroscopy. These sensors might be used for atmospheric purity monitoring as well as for explosives detection. Here, the spectroscopy on sharp vibronic molecular resonances is performed. Therefore the single mode lasers which can be tuned to selected molecular lines are used. Similarly, the spectroscopy at 936 nm was used for sensitive water vapour detection. The opportunity of construction of H₂O sensor reaching the sensitivity about 10 ppb is also discussed.     

Optimization of the mode matching in pulsed cavity ringdown spectroscopy by monitoring non-degenerate transverse mode beating

A simple and reliable method is presented for optimizing the mode matching of a laser beam to the high-finesse cavity used in pulsed cavity ringdown spectroscopy (CRDS). The method is based on minimizing the excitation of higher-order transverse cavity modes through monitoring the non-degenerate transverse mode beating which becomes visible with induced cavity asymmetry caused by slight misalignment. No additional instrument is required other than a pinhole aperture, thus this method can be applied for CRDS experiments in the whole wavelength range. Measurements of the CRDS absorption spectrum of acetylene (C₂H₂) near 571 nm demonstrate that the mode-matching optimization improves the sensitivity of pulsed CRDS. Received: 22 October 2001 / Revised version: 16 January 2002 / Published online: 14 March 2002     

Cavity ring-down spectroscopy of CH and CD radicals in a diamond thin film chemical vapor deposition reactor

A mixture of H₂ and CH₄ is passed over a hot-wire tungsten filament in a diamond thin film chemical vapor deposition reactor. The resulting CH radicals are measured in absorption using cavity ring-down spectroscopy (CRDS). The concentration of the CH radicals increases as the filament is approached. The rotational temperature measurements indicate a large temperature discontinuity between the filament and the CH in the gas phase. The pathways for CH production were investigated by replacing H₂ by D₂ in the feed gas mixture, which resulted in the exclusive production of CD. From this observation it is concluded that rapid H/D isotope exchange dominates in the gas phase. Nonperiodic temporal oscillations in the CH concentration are observed when a rhenium filament is used in place of a tungsten filament. The oscillations are attributed to the nonperiodic changes in the amount of carbon at the filament surface. Received: 21 August 2000 / Accepted: 23 August 2000 / Published online: 23 May 2001     

Cavity ring-down spectroscopy of molecularly thin iodine layers

Cavity ring-down spectroscopy (CRDS) has so far mostly been used for measurements in the gas phase. Only in 1999 was a first spectrum of condensed phase published. This spectrum was measured by using a coated plate between the cavity mirrors. Rather than using this method, our measurements were made using the cavity mirrors as a substrate. This way, the scattering losses could be reduced by approximately a factor of 100. In our measurements we investigated molecularly thin layers of iodine. The iodine spectra were taken in the frequency range from 16200 to 17200 cm^-1 using pulsed CRDS. Received: 14 April 2000 / Revised version: 26 July 2000 / Published online: 22 November 2000     

Intracavity laser absorption spectroscopy of sooting acetylene/air flames

Intracavity laser absorption spectroscopy (ICLAS) is used to measure the absolute concentration profiles of HCO and C₂ in low-pressure acetylene/oxygen/nitrogen flames with equivalence ratios ϕ=0.8, 1.0, 1.5, 2.0 and 2.5. The flames with ϕ=2.0 and 2.5 are soot-producing, with light extinction reaching 0.1% per pass in the flame with ϕ=2.5. This strong broadband extinction does not affect the sensitivity of ICLAS, however. The temperature profiles of the flames were measured using laser-induced fluorescence of the OH radicals. For C₂ concentration measurements, the (0–2) vibronic transition of the Swan band is used. The lines of this transition are located close to the HCO lines, making it possible to measure the two radical concentrations simultaneously. The C₂ concentration is highest in the ϕ=1.5 flame, and lower in the lean and heavily sooted ϕ=2.5 flames. PACS  33.20.Kf; 33.70.Fd; 42.60.Da     

Charge transient spectroscopy measurements of GaAs metal-insulator-semiconductor structures

The Au/Pd/Ti-SiO₂-(n)GaAs structures with and without (NH₄)₂S_x treated gallium arsenide surface, previously analysed by impedance spectroscopy (IS) method, have been investigated using charge transient spectroscopy (QTS) technique. The isothermal QTS spectra of MIS structures kept at room temperature under set of quiescent biases have been recorded in response to both negative and positive pulses of fixed small amplitudes. Two types of charge relaxation characterized by time constant values have been evidenced. The attempt to compare QTS results with ones obtained by impedance spectroscopy method has been presented.     

双腔热解光腔衰荡光谱仪测量大气中NO2和RNO2

A two-channel thermal dissociation cavity ring down spectroscopy (CRDS) instrument has been built for in situ, real-time measurement of NO₂ and total RNO₂ (peroxy nitrates and alkyl nitrates) in ambient air, with a NO₂ detection limit of 0.10 ppbv at 1 s. A 6-day long measurement was conducted at urban site of Hefei by using the CRDS instrument with a time resolution of 3 s. A commercial molybdenum converted chemiluminescence (Mo-CL) instrument was also used for comparison. The average RNO₂ concentration in the 6 days was measured to be 1.94 ppbv. The Mo-CL instrument overestimated the NO₂ concentration by a bias of +1.69 ppbv in average, for the reason that it cannot distinguish RNO₂ from NO₂. The relative bias could be over 100% during the afternoon hours when NO₂ was low but RNO₂ was high.     

Quantum-noise-limited cavity ring-down spectroscopy

We demonstrate a heterodyne-detected cavity ring-down spectroscopy (CRDS) method that allows for a noise-equivalent absorption coefficient of 6 × 10^?14 cm^?1 Hz^?1/2, the lowest which has been reported in a CRDS measurement. It is shown that heterodyne-detected CRDS also reaches the quantum noise limit at reasonable optical powers. In addition to offering ultra-high sensitivity, this technique provides high frequency agility over a range of 2 THz in the near-infrared, which allows entire absorption bands to be recorded in minutes. As a demonstration experiment, high resolution spectra of a near-infrared carbon dioxide band have been recorded.     

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     

Using a DS-DBR laser for widely tunable near-infrared cavity ring-down spectroscopy

Studies into the suitability of a novel, widely tunable telecom L-band (1,563–1,613 nm) digital supermode distributed Bragg reflector (DS-DBR) laser for cavity ring-down spectroscopy (CRDS) are presented. The spectrometer comprised of a 36.6?cm long linear cavity with ring-down times varying between 19–26 μs across the 50 nm DS-DBR wavelength range due to changes in the cavity mirror reflectivities with wavelength. The potential of such a broadband, high-resolution CRD spectrometer was illustrated by investigating several transitions of CO₂ in air, a 5 % calibrated mixture and breath samples. Allan variance measurements at a single wavelength indicated an optimal minimum detectable absorption coefficient (α _min) of 3 × 10^?10 cm^?1 over 20 s.     

Quantification of stable minor species in confined flames by cavity ring-down spectroscopy: application to NO

Cavity ring-down spectroscopy (CRDS) is used to measure the NO mole fraction formed in the burnt gases of low-pressure premixed flames. It is shown that the line-of-sight absorption is greatly increased by the contribution of the NO molecules surrounding the burner. This contribution has been quantified by developing a mathematical procedure taking into account the spatial and spectral features of the CRDS measurement. Calculations have been undertaken in the general case of a stable species not consumed in the flame. The most sensitive parameter is the temperature both in the flame and outside the flame. Simulations allow the selection of the best spectroscopic transitions for a given flame (i.e. a given temperature profile), ensuring the weakest influence of the inaccuracy affecting the temperature determination. High quantum states belonging to the A–X (0–1) band of NO have been found to be the most valuable and have led to a NO mole fraction determination with an accuracy of ±13%. NO absorption in the flame was completely masked using the A–X (0–0) band. Finally, the prompt-NO mole fraction formed in a methane/air flame stabilized at 33 Torr is obtained by combining CRDS and laser induced fluorescence techniques. Received: 12 October / Revised version: 1 February 2002 / Published online: 14 March 2002     

Trace detection of C<Subscript>2</Subscript>H<Subscript>2</Subscript> in ambient air using continuous wave cavity ring-down spectroscopy combined with sample pre-concentration

Continuous wave cavity ring-down spectroscopy (cw-CRDS) coupled with sample pre-concentration has been used to measure acetylene (C₂H₂) mixing ratios in ambient air. Measurements were made in the near-infrared region (λ∼1535.393 nm), using the P(17) rotational line of the (ν₁+ν₃) vibrational combination band, a region free from interference by overlapping spectral absorption features of other air constituents. The spectrometer is shown to be capable of fast, quantitative and precise C₂H₂ mixing ratio determinations without the need for gas chromatographic (GC) separation. The current detection limit of the spectrometer following sample pre-concentration is estimated to be 35 parts per trillion by volume (pptv), which is sufficient for direct atmospheric detection of C₂H₂ at concentrations typical of both urban and rural environments. The CRDS apparatus performance was compared with an instrument using GC separation and flame ionization detection (GC-FID); both techniques were used to analyze air samples collected within and outside the laboratory. These measurements were shown to be in quantitative agreement. The indoor air sample was found to contain C₂H₂ at a mixing ratio of 3.87±0.22 ppbv (3.90±0.23 ppbv by GC-FID), and the C₂H₂ fractions in the outside air samples collected on two separate days from urban locations were 1.83±0.20 and 0.69±0.14 ppbv (1.18±0.09 and 0.60±0.04 ppbv by GC-FID). The discrepancy in the first outdoor air sample is attributed to degradation over a 2-month interval between the cw-CRDS and GC-FID analyses. PACS 82.80.Gk; 39.30.+w; 42.62.Fi; 42.68.Ca     

Studies of thermal decomposition of (NH4)2Fe(SO4)2·6H2O

Thermal decomposition products of the Mohr salt (NH₄)₂Fe(SO₄)₂·6H₂O have been studied and identified using the Mössbauer effect, X-ray diffraction, infrared spectroscopy, and the gravimetric and thermal differential methods. It has been found that the Mohr salt heated for 96 hr. in air at 520K changes to a single substance identified as NH₄Fe(SO₄)₂ with a single Mössbauer line (width 0.30 mm/sec; isomeric shift 0.30 mm/sec). When the Mohr salt is heated for 1 hr. in air at 770 K it changes to Fe₂(SO₄)₃ with a single Mössbauer line (width 0.33 mm/sec; isomeric shift 0.31 mm/sec) strikingly similar to line of NH₄Fe(SO₄)₂.     

Cavity-ring-down spectroscopic studies of NO2 in the region around 613 nm

Catalytic degradation and diffusion processes of NO₂ were followed by cavity-ring-down spectroscopy (CRDS) at 612.9 nm. The suitability of this absorption method for quasi-continuous, direct quantitative measurements over extended periods of time is demonstrated. The high sensitivity of the method is reflected by the fact that NO₂ concentrations as low as 200 ppb were detected at wavelengths at which the absorption of NO₂ is 12-fold lower than at the absorption maximum at 413 nm. Absorption coefficients of less than 1×10^-7 cm^-1 were measured. Received: 25 February 2000 / Revised version: 4 August 2000 / Published online: 5 October 2000     

High sensitivity absorption spectroscopy of HDO by ICLAS-VeCSEL between 9100 and 9640 cm

The absorption spectrum of monodeuterated water has been recorded between 9100 and 9640 cm⁻¹ using intracavity laser absorption spectroscopy (ICLAS) based on a vertical external cavity system emitting laser (VeCSEL). Overall 1706 lines were attributed to the HDO species. The spectrum assignment was performed on the basis of the ab initio calculations by Schwenke and Partridge. A set of 746 energy levels was derived from transitions assigned to 13 upper vibrational states, 300 of them being reported for the first time. Resonance interactions leading to an important strengthening and observations of the very weak 7ν₂ and ν₁ + 5ν₂ bands are discussed. A detailed line list has been generated.     

CARS spectroscopy of molecules and clusters in supersonic jets

Supersonic molecular beams of D₂, CH₄, NH₃, and C₂H₄ are investigated in the expansion region employing collinear coherent anti-Stokes Raman spectroscopy (CARS). The analysis of rotationally resolved CARS spectra allows the determination of temperatures in the beam. The rotational relaxation as a function of stagnation pressure and separation from the nozzle is studied by recording theQ branch for D₂ and the ₃ R andS branches for CH₄. Rotational temperatures for NH₃ are determined by investigating the complete ₃ band. At strong stagnation conditions broad structures arise which can be attributed to the formation of NH₃ clusters. For C₂H₄ the ₅ band with resolved rotational structure is reported. Again, at larger distances from the nozzle, broad structures are observed. They are assigned to the ₁ and ₅ vibrations in the C₂H₄ cluster.     

光腔衰荡光谱法测量大气中的NO3和N2O5

本文应用基于二极管激光器的双路光腔衰荡光谱技术,分别对大气中NO₃和N₂O₅浓度进行监测. 通过使用实验室标准样校正有效吸收腔长比R_L和系统的总损耗系数?,并获得了NO₃有效吸收截面. 该装置在时间分辨率为1 s时,对NO₃的测量灵敏度达到1.1 pptv,N₂O₅被在线转换成NO₃,从而被另一路光腔衰荡光谱装置探测. 利用该装置,对合肥市区冬季夜间大气中的NO₃,N₂O₅浓度进行了实时监测. 通过对比一次大气快速清洁过程中氮氧化物、臭氧、PM_2.5等组分的浓度变化,讨论了大气环境下可能影响NO₃及N₂O₅浓度的因素.     

Ammonia adsorption and decomposition on silica supported Rh nanoparticles observed by in situ attenuated total reflection infrared spectroscopy

Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) is applied to study NH₃, adsorbed from the gas phase, and its decomposition products, i.e. NH_x species, on Rh nanoparticles, produced by spincoating from a RhCl₃ solution in water followed by reduction. A silicon ATR crystal with a hydroxilated SiO₂ layer acts as the support for the nanoparticles. Upon exposure to NH₃ in the vacuum chamber, NH₃ adsorbed to both silica and Rh is detected (sensitivity ∼5 × 10⁻⁵ absorbance units). Interaction of the NH₃ with the silica OH groups is observed around ∼2840 cm⁻¹ in combination with peaks showing the disappearance of unperturbed OH vibrations between 3500 and 3700 cm⁻¹. In addition, NH bend vibrations at 1634 cm⁻¹ and NH stretch vibrations at 3065 and 3197 cm⁻¹ are observed for substrate temperatures between 20 and 100 °C. The latter two correspond to NH on Rh, as verified with a sample without Rh, and probably correspond to undecomposed NH₃. Moreover, they remain after evacuation, suggesting strongly bound species. For a substrate temperature of 75 and 100 °C, additional NH stretch peaks at 3354 and 3283 cm⁻¹ are observed, possibly due to NH₂ intermediates, indicating NH₃ decomposition. It is shown that ATR-FTIR can contribute to the sensitive detection of adsorption and decomposition of gaseous species on realistic planar model catalysts.     

Real-time measurement of nitrogen dioxide in vehicle exhaust gas by mid-infrared cavity ring-down spectroscopy

The application of pulsed cavity ring-down spectroscopy (CRDS) was demonstrated for the measurement of nitrogen dioxide (NO₂) in automotive exhaust gas. The transition of the ν ₃ vibrational band assigned to the antisymmetric stretching mode of NO₂ was probed with a thermoelectrically cooled, pulsed, mid-infrared, distributed feedback, quantum cascade laser (QCL) at 6.13 μm. The measurement of NO₂ in the exhaust gas from two diesel vehicles equipped with different aftertreatment devices was demonstrated using a CRDS-based NO₂ sensor, which employs a HEPA filter and a membrane gas dryer to remove interference from water as well as particulates in the exhaust gas. Stable and sensitive measurement of NO₂ in the exhaust gas was achieved for more than 30 minutes with a time resolution of 1 s.     

Mid-infrared heterodyne phase-sensitive dispersion spectroscopy in flame measurements

We present the first demonstration of heterodyne phase-sensitive dispersion spectroscopy (HPSDS) for in situ, non-intrusive and quantitative CO₂ concentration measurements in flames. Dispersion spectroscopy retrieves gas properties by measuring the refractive index in the vicinity of a molecular resonance. The HPSDS scheme features a significant diagnostic advantage of the intrinsic immunity to laser power fluctuations caused by beam steering, thermal radiation and soot scattering in combustion environments, and thus no extra calibration process is required. In this work, we described the spectroscopic fundamentals for measuring heterodyne phase signals in flames. As a proof of principle, we used a mid-infrared interband cascade laser (ICL) near 4183?nm to exploit the strong CO₂ transitions in the R-branch of the v₃ fundamental band. The HPSDS signals of four CO₂ lines, R(76), R(78), R(80) and R(82), were measured in CH₄/air flames to obtain CO₂ concentrations at different equivalence ratios (Φ?=?0.8–1.2), yielding a good agreement with the simultaneous laser absorption measurements using the same ICL. With its immunity to laser power fluctuations verified experimentally, the HPSDS sensor was successfully implemented to measure CO₂ concentrations in C₂H₄/air sooting flames (Φ?=?1.78–2.38). Laser dispersion spectroscopy proves to be a promising and alternative diagnostic tool for combustion measurements.