Photonic sensing of the atmosphere by absorption spectroscopy

Chemically reactive atmospheric species play a crucial role in tropospheric processes which affect regional air quality and global climate change. Contrary to long-lived species such as greenhouse gases, interference-free accurate and precise concentration assessments of strongly reactive short-lived species represent a real challenge. In this paper, we report on the recent progress in spectroscopic instrumental developments for monitoring of OH, NO₃, HONO and NO₂ by using modern photonic sources (Quantum Cascade Laser, distributed feedback diode laser, light emitting diode) in conjunction with high-sensitivity spectroscopic measurement techniques such as multi-pass cell based long optical path length absorption spectroscopy, wavelength-modulation enhanced off-axis integrated cavity output spectroscopy, Faraday rotation spectroscopy, incoherent broadband cavity enhanced absorption spectroscopy. The main techniques available for routine atmospheric measurements of OH, NO₃ and HONO are overviewed, in comparison with the emerging modern photonic spectroscopy techniques.     

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) in a ring cavity

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) has been demonstrated by coupling a distributed feedback diode laser to a ring cavity. Frequency-selected light decaying from the ring cavity is retro-reflected, inducing a counter-propagating intra-cavity beam, and providing optical feedback to the laser. At specific laser-to-cavity distances, all cavity mode frequencies return to the diode laser with the same phase, allowing spectra to be accumulated across the range of frequencies of the current-tuned laser. OF-CEAS has been used to measure very weak oxygen isotopologue (¹⁶O¹⁸O and ¹⁶O¹⁷O) absorptions in ambient air at wavelengths near 762 nm using the electric-dipole forbidden O₂ A-band. A bandwidth reduced minimum detectable absorption coefficient of 2.2×10⁻⁹ cm⁻¹ Hz^−1/2 is demonstrated.     

Effect of optical feedback noise on tunable diode laser spectroscopy

The effect of optical feedback noise of a laser diode on the stability of gas-absorption spectra was investigated by monitoring the optical absorption of CO₂ gas. Lasing longitudinal mode instability greatly degraded the shape of the absorption spectra, and coherence collapse in the laser diode greatly broadened the spectra. The correlation between the optical feedback noise of the laser diode and the shape of the gas-absorption spectra was clarified on the basis of these spectral behaviors. PACS 42.62.Fi; 42.55.Px; 42.68.Ca     

Characterisation of the potential of frequency modulation and optical feedback locking for cavity-enhanced absorption spectroscopy

A combination of optical feedback self-locking of a continuous-wave distributed feedback diode laser to a V-shaped high finesse cavity, laser phase modulation at a frequency equal to the free spectral range of the V-cavity and detection of the transmitted laser beam at this high modulation frequency is described for the possible application in cavity-enhanced absorption spectroscopy. In order to estimate the noise level of an absorbance baseline, the triplet of frequency modulated light, i.e. the central laser frequency and the two sidebands, were transmitted through both the V-cavity in open air and a 1.5-cm long optical cell placed behind the cavity output mirror and filled with acetylene (C₂H₂) at low pressure. The performance of the setup was evaluated from the measured relative intensity noise on the cavity output (normalised by the bandwidth) and the frequency modulation absorption signals induced by C₂H₂ absorption in the 1.5-cm cell. From these data, we estimate that the noise-equivalent absorption sensitivity of 2.1 × 10^?11 cm^?1 Hz^?1/2—by a factor of 11.7 above the shot-noise limit—can be achieved for C₂H₂ absorption spectra extracted from the heterodyne beat signals recorded at the transmission maxima intensity peaks of the successive TEM₀₀ resonances.     

Signal processing system in cavity enhanced spectroscopy

The paper presents a signal processing system used for nitrogen dioxide detection employing cavity enhanced absorption spectroscopy. In this system, the absorbing gas concentration is determined by the measurement of a decay time of a light pulse trapped in a cavity. The setup includes a resonance optical cavity, which was equipped with spherical and high reflectance mirrors, the pulsed diode laser (414 nm) and electronic signal processing system. In order to ensure registration of low-level signals and accurate decay time measurements, special preamplifier and digital signal processing circuit were developed. Theoretical analyses of main parameters of optical cavity and signal processing system were presented and especially signal-to-noise ratio was taken into consideration. Furthermore, investigation of S/N signal processing system and influence of preamplifier feedback resistance on the useful signal distortion were described. The aim of the experiment was to study potential application of cavity enhanced absorption spectroscopy for construction of fully optoelectronic NO₂ sensor which could replace, e.g., commonly used chemical detectors. Thanks to the developed signal processing system, detection limit of NO₂ sensor reaches the value of 0.2 ppb (absorption coefficient equivalent = 2.8 × 10⁻⁹ cm⁻¹).     

Continuous wave,distributed feedback diode laser based sensor for trace-gas detection of ethane

The development of a continuous wave (CW), thermoelectrically cooled (TEC), distributed feedback (DFB) laser diode based spectroscopic trace-gas sensor for ultra-sensitive and selective ethane (C₂H₆) concentration measurements is reported. The sensor platform used tunable diode laser absorption spectroscopy (TDLAS) based on a 2f wavelength modulation (WM) detection technique. TDLAS was performed with a 100 m optical path length astigmatic Herriott cell. For an interference free C₂H₆ absorption line located at 2976.8 cm⁻¹ a 1σ minimum detection limit of 240 pptv (part per trillion by volume) with a 1 second lock-in amplifier time constant was achieved. In addition, reliable and long-term sensor performance was obtained when operating the sensor in an absorption line locked mode.     

Intra-cavity spectroscopy with diode lasers

A multi-mode diode laser with an external cavity is studied experimentally and theoretically for its application to intra-cavity spectroscopy. One facet of a typical Ga_0.89Al_0.11As laser diode was antireflection-coated by deposition of HfO₂ such that 10^–3 residual reflectivity was left over. This diode was placed in an external optical cavity. The emission spectrum of this diode laser is highly sensitive to any frequency-dependent loss in the cavity, and the detectivity of such a loss grows with the pump rate. Even close to threshold, the absorption at 780 nm of Rb atoms with a density of 5×10¹⁰ cm^–3 has been detected. An adequate model for diode lasers based on rate equations and including frequency-dependent gain saturation is developed and applied to the calculations of output spectra. The sensitivity of these spectra to intra-cavity absorption is determined by the overall cavity loss — which is rather high — and the fraction of spontaneous emission in the total emission, in contrast with dye lasers where it is limited by nonlinear mode coupling. Various criteria for the sensitivity are suggested. The smallest detectable absorption with a perfectly antireflection-coated laser is 10^–6 cm^–1. Improvement of the characteristics of the laser diode would increase the sensitivity.     

CW DFB RT diode laser-based sensor for trace-gas detection of ethane using a novel compact multipass gas absorption cell

The development of a continuous wave, thermoelectrically cooled (TEC), distributed feedback diode laser-based spectroscopic trace-gas sensor for ultra-sensitive and selective ethane (C₂H₆) concentration measurements is reported. The sensor platform used tunable diode laser absorption spectroscopy (TDLAS) and wavelength modulation spectroscopy as the detection technique. TDLAS was performed using an ultra-compact 57.6 m effective optical path length innovative spherical multipass cell capable of 459 passes between two mirrors separated by 12.5 cm and optimized for the 2.5–4 μm range TEC mercury–cadmium–telluride detector. For an interference-free C₂H₆ absorption line located at 2,976.8 cm^?1, a 1σ minimum detection limit of 740 pptv with a 1 s lock-in amplifier time constant was achieved.     

Relaxation effects and high sensitivity photoacoustic detection of NO<Subscript>2</Subscript> with a blue laser diode

A detection limit of 200 ppt of NO₂ in N₂ at atmospheric pressure was obtained with a photoacoustic detector and a high power blue laser diode. This corresponds to a normalized noise (1σ) equivalent absorption coefficient of 2×10^-9 cm^-1W/Hz^0.5. Measurements at different laser modulation frequencies showed no frequency dependence of the photoacoustic signal, indicating a relaxation time τ < 4 μs. Mixing O₂ into the NO₂ containing gas results in a decrease of the photoacoustic signal. A simple model shows that this effect can be attributed to an increased vibrational-vibrational relaxation of NO₂ to O₂. PACS 31.70.Hq; 34.50.Ez; 42.55.Px     

Tm3+/Yb3+共掺铋碲酸盐玻璃中的高效蓝色上转换荧光

制备了高折射率Tm³⁺/Yb³⁺共掺杂铋碲酸盐玻璃，利用棱镜耦合法测量出玻璃在632.8和1550nm波长处的折射率分别为2.0365和1.9795. 对玻璃的吸收、荧光和红外透过光谱展开了测试与分析，根据Judd-Ofelt理论对吸收光谱进行拟合，求得Tm³⁺的振子强度参数Ω_t(t=2，4，6)分别为3.90×10^-20, 2.03×10^-20和9.03×10^{-2 关键词： 3+}/Yb³⁺共掺')" href="#">Tm³⁺/Yb³⁺共掺 铋碲酸盐玻璃 光谱参数 上转换荧光     

Relative line intensity measurement in absorption spectra using a tunable diode laser at 1.6 μm: application to the determination of 13CO2/12CO2 isotope ratio

The measurement of relative intensities in CO₂ combination bands spectrum is performed using wavelength modulation spectroscopy (WMS) and a DFB (distributed feedback) diode laser operating at 1.6 μm. The diode laser is stabilized with an external Fabry–Pérot interferometer and absorption spectroscopy is performed in a multipass gas cell. A spectrum containing spectral lines of both ¹³CO₂ and ¹²CO₂ isotopic species is recorded. The variation of laser power during frequency scanning and the line shape are taken into account to accurately extract line intensities from experimental data. The isotopic concentration ratio is deduced from the intensity ratio. Both ratios are measured with an accuracy of about 0.5% in pure CO₂. Received: 9 June 2000 / Published online: 8 November 2000     

High-resolution laser spectroscopy of ultracold ytterbium atoms using spin-forbidden electric quadrupole transition

We have successfully observed high-resolution spectra of spin-forbidden electric quadrupole transition (¹ S ₀→³ D ₂) in ytterbium (¹⁷⁴Yb) atoms. The differential light shifts between the ¹ S ₀ and the ³ D ₂ states in a far-off resonant trap at 532 nm are also measured. For the spectroscopy, we developed simple, narrow-linewidth, and long-term frequency stabilized violet diode laser systems. Long-term drifts of the excitation laser (404 nm) is suppressed by locking the laser to a length stabilized optical cavity. The optical path length of the cavity is stabilized to another diode laser whose frequency is locked to a strong ¹ S ₀→¹ P ₁ transition (399 nm) of Yb. Both lasers are standard extended-cavity diode lasers (ECDLs) in the Littrow configuration. Since the linewidth of a violet ECDL (～10 MHz) is broader than a typical value of a red or near infra-red ECDL (<1 MHz), we employ optical feedback from a narrow-band Fabry–Perot cavity to reduce the linewidth. The linewidth is expected to be <20 kHz for 1 ms averaging time, and the long-term frequency stability is estimated to be ～200 kHz/h.     

Tunable erbium-doped fiber ring laser for applications of infrared absorption spectroscopy

We fabricate a low noise erbium-doped fiber ring laser that can be continuously tuned over 102 nm by insertion of the fiber Fabry-Perot tunable filter (FFP-TF) in the ring cavity with a novel cavity structure and the optimal gain medium length. As an application of this fiber ring laser, we performed the absorption spectroscopy of acetylene (¹³C₂H₂) and hydrogen cyanide (H¹³C¹⁴N) and measure the absorption spectra of more than 50 transition lines of these gases with an excellent signal to noise ratio (SNR). The pressure broadening coefficients of four acetylene transition lines are obtained using this fiber ring laser and an external cavity laser diode.     

Infrared laser spectroscopy of the CN free radical in a methane-nitrogen-hydrogen plasma

Many Pand R-branch lines of the fundamental bands of the ¹²C¹⁴N and ¹³C¹⁴N radicals in their ground (²Σ⁺) electronic state have been measured at high resolution by diode laser absorption spectroscopy. The radicals were generated in a 2.45 GHz planar microwave plasma in methane with varying proportions of N₂ and H₂. From a fit to the spectra the origins of the fundamental bands of the two isotopomers were determined to be 2042.42104(84) cm^?1 and 2000.084 70(30) cm^?1. The main product detected in the plasma by diode laser spectroscopy is HCN, with concentrations about three orders of magnitude higher than CN.     

Gain versus tuning issues to Q-switch with Yb<Superscript>3+</Superscript>:LSO and amplify broad-bandwidth pulses

We report on the development of Incoherent Broadband Cavity Enhanced Absorption Spectroscopy (IBBCEAS) using a blue light emitting diode (LED) for the detection of NO₂ in laboratory ambient air. Absorption of the oxygen collisional pair in the atmosphere was also detected in the same spectral range. The mirror reflectivity was determined using a standard gas sample mixture of NO₂, and calibrated with the help of the absorption spectrum of the oxygen collisional pair in pure oxygen at atmospheric pressure. Optimization of the experimental parameters was investigated and is discussed in detail. For the first time in IBBCEAS involving broadband absorption spectra, averaging time for signal-to-noise ratio enhancement has been optimized using Allan variance plot. 18.1 ppbv NO₂ in laboratory ambient air has been retrieved from the absorption spectra using differential fitting method over a 40 nm spectral region centered at 470 nm. A minimum detection sensitivity of about 2.2 ppbv (1σ) for NO₂ at atmospheric pressure has been achieved using the optimal averaging time of 100 s by means of a high finesse optical cavity formed with two moderate reflectivity (∼99.55%) mirrors. No purging of the cavity mirrors by high purity He or N₂ gas streams was necessary to prevent contamination of the mirror faces for the in situ measurements.     

Measurements of the temperature and water vapor concentration in a hot zone by tunable diode laser absorption spectrometry

A tunable diode laser absorption spectroscopy (TDLAS) technique and appropriate instrumentation was developed for the measurement of temperature and water vapor concentrations in heated gases. The technique is based on the detection of the spectra of H₂O absorption lines with different energies of low levels. The following absorption lines of H₂O were used: 7189.344 cm⁻¹ (E″=142 cm⁻¹), 7189.541 cm⁻¹ (E″=1255 cm⁻¹), 7189.715 cm⁻¹ (E″=2005 cm⁻¹). Spectra were recorded using fast frequency scanning of a single distributed feedback (DFB) laser. A unique differential scheme for the recording of the absorption spectra was developed. An optimal technique for fitting the experimental spectra was developed.     

Measurements of the atmospheric concentrations of nitrogen dioxide using the radiation absorption in a spectral range of 415 nm

The trace atmospheric concentrations of NO₂ are measured with the methods of the diode laser absorption spectroscopy and the phase shift of the modulated radiation. An electronic transition in a range of 415 nm is employed. For a measurement time of 20 ms, the sensitivity of the concentration measurements is about 10^?11 relative to the concentration of air particles (0.02 ppbv). At a time interval of 5–10 min, the reproducibility of the absolute concentration measurements (0.1 ppbv) is limited by the low-frequency fluctuations of the optical parameters of the spectrometer and the calibration system and corresponds to the level determined by the Allan variance.     

Development of an open-path incoherent broadband cavity-enhanced spectroscopy based instrument for simultaneous measurement of HONO and NO2 in ambient air

We report on the development of an optical instrument based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) for simultaneous open-path measurements of nitrous acid (HONO) and nitrogen dioxide (NO₂) in ambient air using a UV light emitting diode operating at ∼366 nm. Detection limits of ∼430 pptv for HONO and ∼1 ppbv for NO₂ were achieved with an optimum acquisition time of 90 s, determined by an Allan variance analysis. Based on a 1.85 m long high optical finesse open-path cavity, the effective optical path length of 2.8 km was realized in aerosol-free samples or in an urban environment at modest aerosol levels. Such a kilometer long optical absorption is comparable to that achieved in the well established differential optical absorption spectroscopy (DOAS) technology while keeping the instrument very compact. Open-path detection configuration allows one to avoid absorption cell wall losses and sampling induced artifacts. The demonstrated sensitivity and specificity shows high potential of this cost-effective and compact infrastructure for future field applications with high spatial resolution.     

High-sensitivity detection of NO2 using a 740 nm semiconductor diode laser

 An AlGaAs diode laser was used to detect NO₂ absorption lines belonging to the (0 0 0)–(2 13 1) vibrational band, within the X˜² A ₁ electronic ground state, at 739 nm. A simple absorption spectrometer based on wavelength-modulation spectroscopy with second-harmonic detection was developed. The minimum detectable pressure of pure NO₂ was 0.1 μbar with 2 m absorption path-length, corresponding to an absorbance of 10^-6. High-sensitivity detection of NO₂ was also performed in the presence of N₂ and air at different total pressures: The effects on the detection limit of our apparatus were accurately investigated. The minimum NO₂ concentration at 500 mbar of air was measured to be 2 ppm. Received: 11 June 1996 / Revised version: 11 October 1996     

EPR and optical absorption studies of VO doped l-alanine (C3H7NO2) single crystals

VO²⁺ doped l-alanine (C₃H₇NO₂) single crystals and powders are examined by electron paramagnetic resonance (EPR) and optical absorption spectroscopy. Three magnetically different sites are resolved from angular variations of l-alanine single crystal EPR spectra. In some specific orientations each VO²⁺ line splits into three superhyperfine lines with intensities of 1:2:1 and maximum splitting value of 2.23 mT. The local symmetries of VO²⁺ complex sites are nearly axial. The optical absorption spectra show three bands. Spin Hamiltonian parameters are measured and molecular orbital coefficients are calculated by correlating EPR and optical absorption data for the central vanadyl ion.