Integrating sphere effective optical path length calibration by gas absorption spectroscopy

A method of integrating sphere effective optical path length (EOPL) evaluation using tunable diode laser absorption spectroscopy for gas detection was demonstrated. Oxygen was used as a sample gas for an 8.38 cm diameter integrating sphere calibration; 393.7 ± 1.3 cm EOPL was obtained from the wavelength modulation spectroscopy with second harmonic calibration by measuring oxygen P11 line at 764 nm, which is in agreement with that of 393 cm by using direct absorption spectroscopy calibration. The EOPL calibration accuracy of this method can reach 0.33 %. It has been justified that the EOPL of an integrating sphere is independent of the incident light intensity.     

漫反射立方腔单次反射平均光程的理论和实验研究

根据Beer-Lambert定律可知,增加气体池的有效光程是提高气体监测灵敏度最直接而有效的途径.通过实验研究和分析,漫反射立方腔作为气体池能显著地增加有效光程,因此研究其内部的光线传播规律具有重要意义.基于对漫反射立方腔内光线传播规律的理论分析,得到了单次反射平均光程的理论值,建立了漫反射立方腔内光线传播的理论近似模型,并通过有限元法仿真获得了单次反射平均光程的模拟值.利用可调谐二极管激光吸收光谱技术得到了立方腔的有效光程,间接求得了单次反射平均光程的实验值.对理论值、模拟值和实验值进行比较分析,验证了理论近似模型和有限元法仿真的准确性和稳定性.     

Study of optical properties in a cubic quantum dot

In this paper, the effect of hydrostatic pressure on both the intersubband optical absorption coefficients and the refractive index changes is studied for typical GaAs/Al _x  Ga_1?x As cubic quantum dot. We use analytical expressions for the linear and third-order nonlinear intersubband absorption coefficients and refractive index changes obtained by the compact-density matrix formalism. The linear, third-order nonlinear, and total intersubband absorption coefficients and refractive index changes are calculated at different pressures as a function of the photon energy with known values of box length (L), the incident optical intensity (I), and Al concentration (x). According to the results obtained from the present work, we have found that the pressure plays an important role in the intersubband optical absorption coefficient and refractive index changes in a cubic quantum dot.     

Fiber laser intracavity absorption spectroscopy for in situ multicomponent gas analysis in the atmosphere and combustion environments

Intracavity absorption spectroscopy with a broadband Er³⁺-doped fiber laser is applied for the measurements of several molecular species revealing quantitative information about the gas concentration, temperature and chemical reactions in flames. The spectral range of measurements extends from 6200 cm⁻¹ to 6550 cm⁻¹ with the proper choice of the fiber length and by moving an intracavity lens. With a pulsed laser applied in this experiment, the sensitivity to absorption corresponds to an effective absorption path length of 3 km assuming the cavity is completely filled with the sample. For a cw laser, the effective absorption path length is estimated to be 50 km. Absorption spectra of various molecules such as CO₂, CO, H₂O, H₂S, C₂H₂ and OH were recorded separately in the cell and/or in low-pressure methane and propane flames. The presented measurements demonstrate simultaneous in situ detection of three molecular products of chemical reactions at different flame locations. Variation of the relative strengths of OH absorption lines with the temperature enables the estimation of the local flame temperature. The sensitivity of this laser does not depend on the broadband cavity losses and it can be used for in situ measurements of absorption spectra in hostile environments such as contaminated samples, flames or combustion engines. The presented technique can be applied for various diagnostic purposes, such as in environmental, combustion and plasma research, in medicine and in the determination of stable isotope ratios.     

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.     

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     

Study of EVOH based single ion polymer electrolyte: Composition and microstructure effects on the proton conductivity

A comb-like EVOH based single ion polymer electrolyte (EVOH-g-SPEG) was synthesized by sulfonification of EVOH grafts 2-(2-chloroethoxy) ethanol (C₄H₉O₂Cl)/2-[2-(2-chloroethxy) ethoxy] ethanol (C₆H₁₃O₃Cl) with 1, 3-propane sultone. The main chain of the comb-like polymer is hydrophobic polyethylene segments; the side chain is hydrophilic poly (ethylene glycol) (PEG) segment, which can solubilize large amounts of inorganic salts. The sulfonic acid group was introduced onto the end of the PEG side chain. The acid form of SPE was successfully obtained by being dialyzed from the products with acid solution. The saturation water sorption of EVOH-g-SPEG membrane increased with the side chain length and the immersion time. The XRD results indicate that the water in SPE membrane region can destroy the membrane crystalline structure and the water absorption membranes are nearly amorphous. AFM phase images of the hydration membranes clearly show the hydrophilic domains, with sizes increasing from 10 to 35 nm as a function of the side chain length. A phase inversion could be observed when n ≥ 5, which was consistent with a rapid increase in water absorption. And the ion conductivity is also measured by AC impedance. The conductivity is greatly influenced by ion exchange capacity and water sorption. The comb-like EVOH-g-SPEG polymer electrolyte grafts with 2 PEG side chain provides the highest ionic conductivity (1.65 × 10^− 3 S cm^− 1). The comb-like polymer could be a candidate as new polymeric electrolyte material for fuel cells and other electrochemical devices.     

利用离轴腔增强吸收光谱技术探测实际大气中的二氧化碳

以1.573μm窄线宽可调谐半导体激光器作光源,结合高精细度光学谐振腔的离轴腔增强吸收光谱技术,选择CO2在6 357.311 6cm-1的吸收谱线,对实际大气CO2分子进行了测量。为了得到更准确的有效方程,对谐振腔吸收程长的标定方法进行了研究,给出了一种简单、实用的标定方法。实验结果表明,高精密度光学谐振腔的有效吸收程长为～1 195.73m,测得实际大气CO2的浓度为～388.3ppm(S/N≈22),最小可探测浓度为17.65ppm。将波长调制技术与OA-CEAS技术结合后,最终将CO2分子的最小可探测浓度提高到0.36ppm(S/N≈1 064)。     

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     

Line strength and halfwidth measurements from far infrared absorption spectra: Carbon monoxide

A method for deriving Lorentzian line shape parameters (line strengths and halfwidths) from absorption spectra taken at two different path lengths is discussed. Far i.r. absorption spectra of carbon monoxide are analysed to yield line strengths and halfwidths for the rotational transitions J″ = 3 through J>″ = 9. Experimental errors are discussed, and the value for the dipole moment derived from the line strengths, 0·108±0·005 D, is in agreement with the microwave value within experimental uncertainty. The Lorentzian halfwidths are compared, where appropriate, with two recent determinations of these quantities. Lorentzian halfwidths are also derived from absorption spectra taken at long path length using theoretical line strengths based upon μ_co = 0·112D.     

Optische Eigenschaften dünner Cäsium-Schichten im Wellenlängenbereich von 0,3 bis 0,9 μ und ihr elektrischer Widerstand

Electrical resistance and optical transmission, reflexion and absorption of thin films of the alkali metal cesium were measured as a function of thickness, the latter for ∥ and ⊥ polarised monochromatic radiations having wavelengths between 3000 and 9000 Å incident from the vacuum side as well as from the quartz-support side at angles of 45 ° and ca 30 ° resp. The films were prepared by evaporation in static ultra-high vacuum (～10^?10 Torr) onto a cooled (70 K) smooth surface of a thin, plane-parallel plate of polycrystalline quartz. The thickness of the slowly condensing films was varied continuously from zero to some thousand Angström-units corresponding to the bulk metal. The results obtained permit, on the one side, by means of the size effect in the resistance, the determination of the mean free path of the conduction electronsl and of the productp∞ ·l, a constant characterising fundamental electronic properties of the respectiv metal in bulk; they permit, on the other side the identification of the volume- or the surface character of the different plasma oscillations, the determination of their resonance frequency, a quantitative analysis of their development with increasing film thickness, and finally of the optical constants.     

Influences of geometry parameter on mode suppression ratio of fiber grating external cavity semiconductor laser

According to equivalent external cavity approximation model, after taking into account the joint contribution of semiconductor laser, external cavity and fiber grating (FG) to the phase condition, the mode distribution of the fiber grating external cavity semiconductor laser (FGESL) can be determined. As a result, the effect of the FG external cavity length (L) on the side mode suppression ratio (SMSR) of the FGESL is investigated theoretically. The results show that with the injected current and the coupling efficiency increase of the SMSR has taken on rise at all. For strong feedback (R₂ = 10^?4), the SMSR become more flattened with more than 40 dB, but, for weak feedback condition, The SMSR have lesser than 35 dB by an oscillation during rising course. Under the condition of short external cavity, the SMSR is in deep relation to the external cavity length, but the SMSR of longer external cavity is smaller than the SMSR of shorter external cavity on the whole and for 8–11 mm of the external cavity length, the SMSR of the FGESL has better (SMSR > 40.8 dB), and the SMSR become more flattened.     

Optical absorption spectra and EPR g factor of divalent nickel doped magnesia crystal

Based on the crystal- and ligand-field theory, the optical absorption spectra and electron paramagnetic resonance (EPR) g factor of Ni²⁺ ion at Mg²⁺ position in MgO have been investigated. The bond length (i.e. Ni²⁺-O²⁻ distance) was determined from the cubic field parameter Dq; the crystal field Hamiltonian including the spin-orbital (SO) coupling effect of the ligand was diagonalized in the complete basis of 45 wave functions. Results of calculations are in a good agreement with experimental data.     

A build-up cavity for Fourier transform emission experiments

We have recorded electronic spectra of some diatomic species (I₂, K₂, and NaK), to illustrate the potential power of the combination of two high resolution techniques: intra-cavity laser induced fluorescence (ICLIF) and Fourier transform (FT) spectroscopy. Active and passive optical cavities have been used, working with visible continuous wave (cw) laser sources. The active cavity is a modified commercial ring dye laser, allowing for a sample up to 25 cm in length. Dispersed fluorescence spectra recorded on a Bomem Fourier transform spectrometer showed a signal enhancement of about 10 when a molecular source was placed within the resonator. The system was tested with a heatpipe source, producing alkali metal vapour at about 300 °C. These experiments illustrate enhanced cascade excitation mechanisms in K₂; the highest vibrational levels of the electronic ground state of K₂ can be observed with surprising ease. The increase in available power within the cavity has also led to the observation of fluorescence in NaK excited by a two-photon transition (Q (66) 6¹Σ⁺ ← X¹Σ⁺ transition). Spatial limitations have driven us to build a more versatile ring cavity able to accommodate larger sources. This broad-band (590-650 nm) build-up cavity is locked by a Hänsch-Couillaud servo-loop to an input laser of (instantaneous) bandwidth ∼1 MHz. Power enhancement factors of around 30 have been obtained with a 2.6% input coupler. The performance of the build-up cavity has been tested by recording FT spectra of intra-cavity laser induced fluorescence of iodine. The technique clearly has useful applications for weakly absorbing species, or for those whose electronic states are inaccessible to single-photon absorption techniques. This paper describes the arrangement we have used, highlighting some of the advantages and describing some of the particular difficulties we have encountered.     

VCSEL-based oxygen spectroscopy for structural analysis of pharmaceutical solids

We present a minimalistic and flexible single-beam instrumentation based on sensitive tunable diode laser absorption spectroscopy (TDLAS) and its use in structural analysis of highly scattering pharmaceutical solids. By utilising a vertical cavity surface emitting laser (VCSEL) for sensing of molecular oxygen dispersed in tablets, we address structural properties such as porosity. Experiments involve working with unknown path lengths, severe backscattering and diffuse light. These unusual experimental conditions has led to the use of the term gas in scattering media absorption spectroscopy (GASMAS). By employing fully digital wavelength modulation spectroscopy and coherent sampling, system sensitivity in ambient air experiments reaches the 10^-7 range. Oxygen absorption exhibited by our tablets, being influenced by both sample porosity and scattering, was in the range 8×10^-5 to 2×10^-3, and corresponds to 2–50 mm of path length through ambient air (L_eq). The day-to-day reproducibility was on average 1.8% (0.3 mm L_eq), being limited by mechanical positioning. This is the first time sub-millimetre sensitivity is reached in GASMAS. We also demonstrate measurements on gas transport on a 1-s time scale. By employing pulsed illumination and time-correlated single-photon counting, we reveal that GASMAS exhibits excellent correlation with time-domain photon migration. In addition, we introduce an optical measure of porosity by relating oxygen absorption to average photon time-of-flight. Finally, the simplicity, robustness and low cost of this novel TDLAS instrumentation provide industrial potential. PACS 42.62.Fi; 39.30.+w; 78.55.Mb; 42.62.Cf; 87.64.Cc     

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.     

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.     

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.     

TDLAS-based open-path laser hygrometer using simple reflective foils as scattering targets

We present a new, very simple to use and very easy to align, inexpensive, robust, mono-static optical hygrometer based on tunable diode laser absorption spectroscopy (TDLAS) that makes use of very inexpensive reflective foils as scattering targets at the distant side of the absorption path. Various alternative foils as scattering targets were examined concerning their reflective behaviour and their suitability for TDLAS applications. Using a micro prismatic reflection tape as the optimum scattering target we determined absolute water vapour concentrations employing open path TDLAS. With the reflection tape being in a distance of 75?cm to 1?m (i.e., absorption path lengths between 1.5 and 2?m) we detected ambient H₂O concentrations of up to 12,300?ppmv with detectivities of 1?ppm which corresponds to length and bandwidth normalized H₂O detection limits of up to 0.9?ppmv?m/ $ \sqrt {\text{Hz}} $ , which is only a factor of 2 worse than our previous bi-static TDLAS setups (Hunsmann, Appl. Phys. B 92:393?C401, 1). This small sensitivity disadvantage is well compensated for by the simplicity of the spectrometer setup and particularly by its extreme tolerance towards misalignment of the scattering target.     

腔增强吸收光谱技术中的腔镜反射率标定方法研究

腔增强吸收光谱技术具有实验装置相对简单、灵敏度高、环境适应性强等特点,是高灵敏吸收光谱技术的重要分支之一,在其应用过程中,腔镜反射率是影响其测量准确性的重要因素。利用2.0 μm可调谐二极管激光器作为光源搭建了一套腔增强吸收光谱测量系统,使用两片反射率为99.9%的高反镜作为腔镜,以CO₂气体在5 001.49 cm-1处的吸收谱线作为研究目标,对两种简单实用的腔镜反射率标定方法进行了对比研究。第一种标定方法利用已知程长多通池作为参考池,通过测量谐振腔和多通参考池的输出吸收信号,比较二者的吸收率推导出腔增强系统中的有效吸收路径,然后通过镜片反射率和有效吸收路径的关系对腔镜反射率进行标定;第二种标定方法根据理想气体状态方程得到气体分子数密度,并结合数据库中的谱线线强值,实现了对腔镜反射率进行标定。结果表明,方法一中积分腔与参考池测得信号的积分吸收面积之比为10.5,经过多次测量并计算得到积分腔的有效吸收路径与镜片的反射率分别为302.65 m和99.85%,得到大气中CO₂气体的浓度为0.037 3%,与实际大气CO₂的含量相符合,验证了此方法的准确性;该方法的优点是不受样品浓度影响,但因引入新的参考池,需要两池中气体的压强和温度都保持一致,此方法适用于开放式的腔体结构。方法二中测得大气中CO₂分子位于5 001.49 cm-1处吸收光谱,并结合大气中CO₂气体的分子数密度N为9.099×1015 molecule·cm-3,Hitran数据库中该条谱线线强为3.902×10-22 cm·molecule-1,计算得到镜片反射率约为99.84%;此方法优点是结构相较前一种方法更简单,但需要已知被测气体的分子数密度,因此在配置气体的过程中浓度、压力的误差会影响腔镜反射率的标定。由此可见两种镜片标定方法均可精确实现对腔镜反射率的标定,根据两种方法的特点,在实际应用中可选取相应适合的方法作为参考。