Application of a broadband blue laser diode to trace NO2 detection using off-beam quartz-enhanced photoacoustic spectroscopy

We applied for the first time, to our knowledge, broadband off-beam quartz-enhanced photoacoustic spectroscopy (BB-OB-QEPAS) to trace NO2 detection using a broadband blue laser diode centered at 450?nm. A detection limit of 18?ppbv (parts in 10(9) by volume) for NO2 in N2 at atmospheric pressure was achieved with an average laser power of 7?mW at a 1?s integration time, which corresponds to a 1?σ normalized noise equivalent absorption coefficient of 4.1×10(-9) cm(-1)?W=Hz(1=2). An Allan variance analysis was performed to investigate the long-term stability of the BB-OB-QEPAS-based NO2 sensor.     

Cavity ringdown spectroscopy using mid-infrared quantum-cascade lasers

Cavity ringdown spectra of ammonia at 10 parts in 10(9) by volume (ppbv) and higher concentrations were recorded by use of a 16-mW continuous-wave quantum-casacde distributed-feedback laser at 8.5 mum whose wavelength was continuously temperature tuned over 15 nm. A sensitivity (noise-equivalent absorbance) of 3.4x10(-9) cm(-1) Hz(-1/2) was achieved for ammonia in nitrogen at standard temperature and pressure, which corresponds to a detection limit of 0.25 ppbv.     

Ultra-sensitive carbon monoxide detection by using EC-QCL based quartz-enhanced photoacoustic spectroscopy

A quartz-enhanced photoacoustic spectroscopy (QEPAS) based sensor for carbon monoxide detection at ppbv levels was developed with a 4.65???m external-cavity quantum cascade laser operating both in continuous wave (cw) and pulsed modes. A?23-fold enhancement of the measured CO signal amplitude was obtained when water vapor, acting as a catalyst for vibrational energy transfer, was added to the targeted analyte mixture. In the cw mode, a noise-equivalent sensitivity (NES, 1??) of 2 ppbv was achieved at a gas pressure of 100?Torr, for 1-s lock-in amplifier (LIA) time constant (TC), which corresponds to a normalized noise equivalent absorption coefficient (NNEA) of $1.48\times 10^{-8}~\mathrm{cm}^{-1}\,\mathrm{W}/\sqrt{\mathrm{Hz}}$ . In the pulsed mode, the determined NES and NNEA were 46?ppbv and $1.07\times 10^{-8}~\mathrm{cm}^{-1}\,\mathrm{W}/\sqrt{\mathrm{Hz}}$ , respectively, for a 3-ms LIA TC at atmospheric pressure with a laser scan rate of 18?cm^-1/s and a 50?% duty cycle. An intercomparison between cw and pulsed QEPAS-based CO detection is also reported.     

Time resolved simultaneous detection of 14NO and 15NO via mid-infrared cavity leak-out spectroscopy

We present a ring-down absorption spectrometer based on a continuous-wave CO laser in the mid-infrared spectral region near lambda = 5 microm. Using a linear ring-down cavity (length: 0.5 m) with high reflective mirrors (R = 99.988 %), we observed a noise-equivalent absorption coefficient of 3 x 10(-10) cm(-1)Hz(-1/2). This corresponds to a noise-equivalent concentration of 800 parts per trillion (ppt) for (14)NO and 40 ppt for (15)NO in 1 s averaging time. We achieve a time resolution of 1 s which allows time resolved simultaneous detection of the two N isotopes. The delta(15)N value was obtained with a precision of +/-1.2 per thousand in a sample with a NO fraction of 11 ppm. The simultaneous detection enables the use of (15)NO as a tracer molecule for endogenous biomedical processes.     

LP-DOAS测量乙二醛时大气中干扰吸收的去除(英文)

针对利用长光程差分吸收光谱技术在实现对大气中乙二醛实时监测中,一些干扰结构(Xe灯结构,H2O、NO2和O4干扰吸收)对长光程差分吸收光谱技术的影响,讨论了乙二醛的光谱反演方法对干扰吸收的准确去除.针对Xe灯结构由于压力和多普勒展宽程度等的变化而引起的Xe灯结构的非线性变化,采用不同时刻的参考灯谱通过光谱插值的方式准确去除,其去除误差引起的剩余结构可降低到比乙二醛的最低理论检测限低3倍;针对H2O的非线性吸收以及特征吸收结构随柱浓度的不同而变化的特点,采用较高和较低浓度H2O吸收光谱插值的方法准确去除了严重干扰乙二醛准确反演的H2O的吸收结构,其去除误差引起的剩余结构可降低到比乙二醛的最低理论检测限低10倍;另外,对于在此波段存在干扰的NO2和O4的吸收结构也实现了准确地去除.干扰结构的准确去除使DOAS对乙二醛的监测实现了较低的实际检测限(0.15ppbv)和较低的测量误差(～10%).最后,在广州郊区对实际大气进行了实际监测,其浓度范围在低于检测限到1.66ppbv之间,与文献报道的浓度范围和变化趋势十分吻合.     

LP-DOAS测量乙二醛时大气中干扰吸收的去除

针对利用长光程差分吸收光谱技术在实现对大气中乙二醛实时监测中,一些干扰结构（Xe灯结构,H2O、NO2和O4干扰吸收）对长光程差分吸收光谱技术的影响,讨论了乙二醛的光谱反演方法对干扰吸收的准确去除.针对Xe灯结构由于压力和多普勒展宽程度等的变化而引起的Xe灯结构的非线性变化,采用不同时刻的参考灯谱通过光谱插值的方式准确去除,其去除误差引起的剩余结构可降低到比乙二醛的最低理论检测限低3倍|针对H2O的非线性吸收以及特征吸收结构随柱浓度的不同而变化的特点,采用较高和较低浓度H2O吸收光谱插值的方法准确去除了严重干扰乙二醛准确反演的H2O的吸收结构,其去除误差引起的剩余结构可降低到比乙二醛的最低理论检测限低10倍|另外,对于在此波段存在干扰的NO2和O4的吸收结构也实现了准确地去除.干扰结构的准确去除使DOAS对乙二醛的监测实现了较低的实际检测限 (0.15 ppbv)和较低的测量误差 (~10 %).最后,在广州郊区对实际大气进行了实际监测,其浓度范围在低于检测限到1.66 ppbv之间,与文献报道的浓度范围和变化趋势十分吻合.     

Trace Moisture Measurement with 5. 2 mu m Quantum Cascade Laser Based Continuous-Wave Cavity Ring-Down SpectroscopyEI北大核心CSCD

Trace moisture concentration in high-purity gases is an important parameter in semiconductor manufacturing because many manufacturing processes are sensitive to moisture even on the level of parts per billion by volume (ppbv). Detection of trace moisture in mid-infrared spectral region is beneficial due to more abundant and stronger spectral lines in this region. Recently, Quantum cascade lasers (QCLs) with high output power, narrow line-width, and high reliability have been developing rapidly and have become promising light sources for sensitive spectroscopic measurements. By employing a 5. 2 mu m external-cavity tunable quantum cascade laser, a continuous-wave cavity ring-down spectroscopy (CRDS) experimental setup is established and applied to detect trace moisture in high-purity nitrogen gas. In the experiment, the CRDS signal is averaged to improve the detection sensitivity, and the optimal averaging number is determined by Allan variance calculation to be 602. For trace moisture detection, the absorption cross-section of H2O in the spectral range between 1 905 and 1 925 cm(-1) is simulated according to the HITRAN database and the optimal detection spectral line is chosen. Detected at 1 918 cm(-1) absorption line at 296 K temperature and 1 atm pressure, the measured moisture concentration is in good agreement with the nominal value, and the minimum detectable moisture concentration of 24. 8 ppbv is achieved when cavity mirrors with reflectance of 99.93% are used. The experimental results show that mid-infrared cavity ring-down spectroscopy technique has great potential in a wide variety of applications, such as industrial production control, environmental monitoring and health diagnosis, etc.     

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-ppbv nitric oxide concentration measurements using cw thermoelectrically cooled quantum cascade laser-based integrated cavity output spectroscopy

A nitric oxide (NO) gas sensor based on a thermoelectrically cooled, continuous-wave, distributed feedback quantum cascade laser operating at 5.45 μm (1835 cm^-1) and off-axis integrated cavity output spectroscopy combined with a wavelength-modulation technique was developed to determine NO concentrations at the sub-ppbv levels that are essential for a number of applications, such as medical diagnostics, environmental monitoring, and industrial process control. The sensor employs a 50-cm-long high-finesse optical cavity that provides an effective path length of ∼700 m. A noise equivalent (SNR=1) minimum detection limit of 0.7 ppbv with a 1-s observation time was achieved. PACS 07.07.Df; 33.20.Ea; 42.62.Fi; 87.64.Je     

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     

High-sensitivity intracavity laser absorption spectroscopy with vertical-external-cavity surface-emitting semiconductor lasers

We report the demonstration of high-sensitivity intracavity laser absorption spectroscopy with multiple-quantum-well vertical-external-cavity surface-emitting semiconductor lasers (VECSEL's). A detection limit of 3x10(-10) cm (-1) has been achieved. The spectrotemporal dynamics of a VECSEL in the 1030-nm wavelength region has been studied. The laser was operating cw at room temperature, with a baseline signal-to-noise ratio as high as 400. The laser was optically pumped with a threshold as low as 80 mW and was broadly tunable over a spectral range of ~75 nm .     

Optical parametric oscillator based off-axis integrated cavity output spectroscopy for rapid chemical sensing

An optical parametric oscillator (OPO), pumped by a fiber-amplified diode laser, is combined with off-axis integrated cavity output spectroscopy (OA-ICOS). The cw OPO (power 1.2 W, tunability 3-4 μm, 5 cm(-1) mode-hop-free tuning) has a tuning speed of 100 THz/s, which is ideal for rapid and sensitive trace gas detection. Combined with OA-ICOS, a detection limit of 50 parts per trillion by volume (1×10(12)) of ethane (C(2)H(6)) in nitrogen was obtained in 0.25s at 2997 cm(-1), corresponding to a noise equivalent absorption sensitivity of 4.8×10(-11) cm(-1) Hz(-1/2). The system demonstrates real-time measurements of methane and water in exhaled human breath.     

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     

1.315 μm波长附近实际大气高分辨率吸收光谱

 用窄线宽、脉冲可调谐光参量振荡器（OPO）作光源，使用光程长达1 097m的怀特池，采用单探测器分时复用的探测方法，首次在吸收池中精确测量了实际大气中1.315 μm波长附近高分辨率吸收光谱，实验验证了实际大气中水汽是该波段的主要吸收气体；得到了实际大气中吸收分子在氧碘激光波长（7 603.14cm^-11）处的吸收截面为 (1.05±0.09)×10^-24 cm²(标准大气条件下）以及在该波段主要吸收谱线的参数，包括吸收线的位置、线强度、压力加宽半宽度等。利用实测的线参数计算了在氧碘激光波长附近大气分子的吸收截面，发现吸收最小的波长分别位于7 603.31和7 603.93cm^-1，其值约为(8.9±0.8)×10^-25 cm²，比氧碘激光波长处的吸收截面约小15%。     

Cavity-enhanced absorption spectroscopy with a red LED source for NOx trace analysis

Incoherent broad-band cavity-enhanced absorption spectroscopy (IBB-CEAS) based on arc lamps has been around for a few years, but only two reports exist using light-emitting diodes (LEDs). We present a setup based on a 643-nm LED which is of interest for the simultaneous detection of NO₃ and NO₂. The latter is chosen for testing as it is stable and available in calibrated diluted samples. A detection limit in the ppbv range is obtained with 2-min averaging (5×10^-9 /cm rms baseline noise level), comparable to the best performance of chemiluminescence devices used for pollution monitoring. At 1-s acquisition time, the detection limit is below 10 ppbv. Extrapolation to NO₃ yields a detection limit of a few pptv for a few minutes averaging. We also test the retrieval of absolute sample absorption (and concentration) using the cavity mirror reflectivity obtained with a commercial spectrophotometer, and we conclude that a calibration based on a reference sample of known concentration is preferable for accurate concentration measurements with IBB-CEAS. Finally, we present a rigorous frequency-domain derivation of cavity transmission as a function of wavelength for a broad-band spectrally smooth source, which complements the time-domain derivation by Fiedler et al. This derivation exposes an issue with multiple transverse mode excitation inherent to this technique, which may result in slightly distorted spectral profiles. PACS 07.88.+y; 07.60.Rd; 42.60.Da     

Optical-feedback cavity-enhanced absorption spectroscopy with a quantum cascade laser

Optical-feedback cavity-enhanced absorption spectroscopy is demonstrated in the mid-IR by using a quantum cascade laser (emitting at 4.46 μm). The laser linewidth reduction and frequency locking by selective optical feedback from the resonant cavity field turns out to be particularly advantageous in this spectral range: It allows strong cavity transmission, which compensates for low light sensitivity, especially when using room-temperature detectors. We obtain a noise equivalent absorption coefficient of 3 × 10(-9)/cm for 1 s averaging of spectra composed by 100 independent points. At 4.46 μm, this yields a detection limit of 35 parts in 10(12) by volume for N(2)O at 50 mbar, corresponding to 4 × 10(7) molecules/cm(3), or still to 1 fmol in the sample volume.     

1．3μm附近CO2的高灵敏度吸收光谱

采用可连续调谐半导体二极管激光器作为探测光源,将长程多通池吸收光谱、波长调制和谐波探测技术相结合,建立了一套具有高检测灵敏度和高分辨率的测量气态分子光谱及进行微量分析的研究装置.可以测量6.67×102Pa下～10-27 cm-1·(molecule·cm-2)-1的强度,最小可探测吸收达到～10-8.并利用该装置测量了CO2气体在1.31 μm附近的近红外吸收光谱,并用最小二乘法拟合实验数据获得了这一波段谱线的参数.同时测量的谱线参数与HITRAN数据库相比,发现15条数据库上没有报道的弱谱线.     

Photoacoustic spectroscopy of formaldehyde with tunable laser radiation at the parts per billion level

Selective and sensitive detection of formaldehyde (CH₂O) was achieved using a grazing-incidence optical parametric oscillator (GIOPO), pumped at high repetition rate, as a light source for photoacoustic spectroscopy. The photoacoustic spectrum of formaldehyde was measured in the range from 2785 to 2840 cm^-1 and an absorption line at 2805.0 cm^-1 was selected for detection. Concentrations down to 20 ppbv (parts per billion by volume) formaldehyde in nitrogen were recorded. The detection limit determined by background fluctuations was 3 ppbv (S/N=1) for 3 s lock-in time constant and 3 min acquisition time. The 2805.0 cm^-1 absorption line of the ν₁ vibrational mode was chosen because of the absence of interference with water and carbon-dioxide bands. This allowed the direct detection of formaldehyde in laboratory air without filtering. PACS 42.62.Fi; 42.68.Ca; 42.65.Yj; 07.07.Df     

高灵敏的连续激光光腔衰荡光谱仪及其应用

基于连续可调谐的钛宝石激光光源,建立了光腔衰荡光谱(CRDS)装置,实验表明,其不但具有10-4cm-1的光谱分辨率,测靖灵敏度也好于10-10·cm-1.通过对C2H2气体在12 696.4 cm-1附近的吸收光谱测量,验证了该装置的定量测量能力,并通过对混有痕量C2H2气体的氮气样品的光谱测量,表明该装置对C2H2...