Diode laser measurement of line strengths and air-broadening coefficients of CO2 and CO in the 1.57 μm region for combustion diagnostics

Spectral measurements of two line pairs of CO₂ and CO in the temperature range 300–1000 K at 1.573 µm were performed using a fiber-coupled distributed feedback (DFB) diode laser. The two line pairs can be used in a tunable diode laser (TDL) absorption sensor for simultaneously detecting CO₂ and CO gas in a single scan of the diode laser. The spectral parameters (line strengths, air-broadening coefficients and the temperature exponent n) of the two pairs are presented. The measured data agree well with existing databases (HITRAN 2004 and HITRAN 2008), the discrepancies being less than 5% for most of the probed transitions. Although the HITRAN database is a useful tool for sensor design, we found that laboratory measurements of the spectroscopic data for the line pair selected for high-temperature sensors are necessary for establishing the uncertainty for accurate measurements.     

Development of a fast temperature sensor for combustion gases using a single tunable diode laser

The 12 best NIR water transition line pairs for temperature measurements with a single DFB laser in flames are determined by systematic analysis of the HITRAN simulation of the water spectra in the 1–2 μm spectral region. A specific line pair near 1.4 μm was targeted for non-intrusive measurements of gas temperature in combustion systems using a scanned-wavelength technique with wavelength modulation and 2f detection. This sensor uses a single diode laser (distributed-feedback), operating near 1.4 μm and is wavelength scanned over a pair of H₂O absorption transitions (7154.354 cm^-1 & 7153.748 cm^-1) at a 2 kHz repetition rate. The wavelength is modulated (f=500 kHz) with modulation amplitude a=0.056 cm^-1. Gas temperature is inferred from the ratio of the second harmonic signals of the two selected H₂O transitions. The fiber-coupled-single-laser design makes the system compact, rugged, low cost and simple to assemble. As part of the sensor development effort, design rules were applied to optimize the line selection, and fundamental spectroscopic parameters of the selected transitions were determined via laboratory measurements including the temperature-dependent line strength, self-broadening coefficients, and air-broadening coefficients. The new sensor design includes considerations of hardware and software to enable fast data acquisition and analysis; a temperature readout rate of 2 kHz was demonstrated for measurements in a laboratory flame at atmospheric pressure. The combination of scanned-wavelength and wavelength-modulation minimizes interference from emission and beam steering, resulting in a robust temperature sensor that is promising for combustion control applications.PACS 42.62.Fi; 42.55.Px; 42.60.Fc; 39.30+w     

Near-infrared diode laser absorption sensor for rapid measurements of temperature and water vapor in a shock tube

A fast-response (100 kHz) tunable diode laser absorption sensor is developed for measurements of temperature and H₂O concentration in shock tubes, e.g. for studies of combustion chemistry. Gas temperature is determined from the ratio of fixed-wavelength laser absorption of two H₂O transitions near 7185.60 cm^-1 and 7154.35 cm^-1, which are selected using design rules for the target temperature range of 1000–2000 K and pressure range of 1–2 atm. Wavelength modulation spectroscopy is employed with second-harmonic detection (WMS-2f) to improve the sensor sensitivity and accuracy. Normalization of the second-harmonic signal by the first-harmonic signal is used to remove the need for calibration and minimize interference from emission, scattering, beam steering, and window fouling. The laser modulation depth for each H₂O transition is optimized to maximize the WMS-2f signal for the target test conditions. The WMS-2f sensor is first validated in mixtures of H₂O and Ar in a heated cell for the temperature range of 500–1200 K (P=1 atm), yielding an accuracy of 1.9% for temperature and 1.4% for H₂O concentration measurements. Shock wave tests with non-reactive H₂O–Ar mixtures are then conducted to demonstrate the sensor accuracy (1.5% for temperature and 1.4% for H₂O concentration) and response time at higher temperatures (1200–1700 K, P=1.3–1.6 atm). PACS 42.62.Fi; 42.55.Px; 42.60.Fc; 07.35.+k     

Measurements of high-pressure CO2 absorption near 2.0 μm and implications on tunable diode laser sensor design

A tunable diode laser (TDL) is used to measure the absorption spectra of the R46 through R54 transitions of the 20012←00001 band of CO₂ near 2.0 μm (5000 cm⁻¹) at room temperature and pressures to 10 atm (densities to 9.2 amagat). Spectra are recorded using direct absorption spectroscopy and wavelength modulation spectroscopy with second-harmonic detection (WMS-2f) in a mixture containing 11% CO₂ in air. The direct absorption spectra are influenced by non-Lorentzian effects including finite-duration collisions which perturb far-wing absorption, and an empirical χ-function correction to the Voigt line shape is shown to greatly reduce error in the spectral model. WMS-2f spectra are shown to be at least a factor of four less-influenced by non-Lorentzian effects in this region, making this approach more resistant to errors in the far-wing line shape model and allowing a comparison between the spectral parameters of HITRAN and a new database which includes pressure-induced shift coefficients. The implications of these measurements on practical, high-pressure CO₂ sensor design are discussed.     

CO2 concentration and temperature sensor for combustion gases using diode-laser absorption near 2.7 μm

A new tunable diode-laser sensor based on CO₂ absorption near 2.7 μm is developed for high-resolution absorption measurements of CO₂ concentration and temperature. The sensor probes the R(28) and P(70) transitions of the ν₁+ν₃ combination band of CO₂ that has stronger absorption line-strengths than the bands near 1.5 μm and 2.0 μm used previously to sense CO₂ in combustion gases. The increased absorption strength of transitions in this new wavelength range provides greatly enhanced sensitivity and the potential for accurate measurements in combustion gases with short optical path lengths. Simulated high-temperature spectra are surveyed to find candidate CO₂ transitions isolated from water vapor interference. Measurements of line-strength, line position, and collisional broadening parameters are carried out for candidate CO₂ transitions in a heated static cell as a function of temperature and compared to literature values. The accuracy of a fixed-wavelength CO₂ absorption sensor is determined via measurement of known temperature and CO₂ mole fraction in a static cell and shock-tube. Absorption measurements of CO₂ are then made in a laboratory flat-flame burner and in ignition experiments of shock-heated n-heptane/O₂/argon mixtures to illustrate the potential of this sensor for combustion and reacting-flow applications. PACS 42.62.Fi; 42.55.Px; 07.07.Df     

Number density and temperature measurements obtained using sensitive diode laser spectroscopy in an argon plasma

The absolute concentration and translational temperature of the 2p₁₀ and 2p₇ excited states of argon have been measured in an inductively coupled plasma chamber under a variety of operating conditions using both calibrated diode laser frequency modulation spectroscopy and cavity enhanced absorption spectroscopy. Accurate lineshape analysis of frequency modulation signals has been employed to extract the desired information, and is corroborated by cavity enhanced measurements. Temperatures are found to vary linearly with pressure from ∼400 K at 20 mTorr (2.7 Pa) to ∼510 K at 90 mTorr (12 Pa) in a 200 W discharge while concentrations peak at 3.25×10⁸ cm^-3 at 30 mTorr (4 Pa) (also in a 200 W discharge). The uncertainty in the recovered temperature is 7%, dominated by uncertainties in the calibration of the frequency scale. PACS 42.62Fi; 52.70kz     

Experimental study of H2O spectroscopic parameters in the near-IR (6940-7440 cm) for gas sensing applications at elevated temperature

Tunable diode laser (TDL) absorption sensors of water vapor are attractive for temperature, gas composition, velocity, pressure, and mass flux measurements in a variety of practical applications including hydrocarbon-fueled combustion systems. Optimized design of these sensors requires a complete catalog of the assigned transitions with accurate spectroscopic data; our particular interest has been in the 2ν₁, 2ν₃, and ν₁+ν₃ bands in the near-IR where telecommunications diode lasers are available. In support of this need, fully resolved absorption spectra of H₂O vapor in the spectral range of 6940-7440 cm⁻¹ (1344-1441 nm) have been measured as a function of temperature (296-1000 K) and pressure (1-800 Torr), and quantitative spectroscopic parameters inferred from these spectra compared to published data from Toth, HITRAN 2000 and HITRAN 2004. The peak absorbances were measured for more than 100 strong transitions at 296 and 828 K, and linestrengths determined for 47 strong lines in this region. In addition to reference linestrengths S(296 K), the air-broadening coefficients γ_air(296 K) and temperature exponents n were inferred for strong transitions in five narrow regions, near 7185.60, 7203.89, 7405.11, 7426.14 and 7435.62 cm⁻¹ that had been targeted as attractive for future diagnostics applications. Most of the measured results, determined within an accuracy of 5%, are found to be in better agreement with HITRAN 2004 than with earlier editions of this database. Large discrepancies (>10%) between measurements and HITRAN 2004 database are identified for some of the probed transitions. These new spectroscopic data for H₂O provide a useful test of the sensor design capabilities of HITRAN 2004 for combustion and other applications at elevated temperatures.     

Measurements of near-IR water vapor absorption at high pressure and temperature

Tunable diode lasers (TDLs) are used to measure high resolution (0.1 cm^-1), near-infrared (NIR) water vapor absorption spectra at 700 K and pressures up to 30 atm within a high-pressure and -temperature optical cell in a high-uniformity tube furnace. Both direct absorption and wavelength modulation with second harmonic detection (WMS-2f) spectra are obtained for 6 cm^-1 regions near 7204 cm^-1 and 7435 cm^-1. Direct absorption measurements at 700 K and 10 atm are compared with simulations using spectral parameters from HITRAN and a hybrid database combining HITRAN with measured spectral constants for transitions in the two target spectral regions. The hybrid database reduces RMS error between the simulation and the measurements by 45% for the 7204 cm^-1 region and 28% for the 7435 cm^-1 region. At pressures above 10 atm, the breakdown of the impact approximation inherent to the Lorentzian line shape model becomes apparent in the direct absorption spectra, and measured results are in agreement with model results and trends at elevated temperatures reported in the literature. The wavelength-modulation spectra are shown to be less affected by the breakdown of the impact approximation and measurements agree well with the hybrid database predictions to higher pressures (30 atm). PACS 33.20.Ea; 42.62.Fi; 52.25.Os     

Sensitive detection of temperature behind reflected shock waves using wavelength modulation spectroscopy of CO2 near 2.7?μm

Tunable diode-laser absorption of CO₂ near 2.7 μm incorporating wavelength modulation spectroscopy with second-harmonic detection (WMS-2f) is used to provide a new sensor for sensitive and accurate measurement of the temperature behind reflected shock waves in a shock-tube. The temperature is inferred from the ratio of 2f signals for two selected absorption transitions, at 3633.08 and 3645.56 cm⁻¹, belonging to the ν ₁+ν ₃ combination vibrational band of CO₂ near 2.7 μm. The modulation depths of 0.078 and 0.063 cm⁻¹ are optimized for the target conditions of the shock-heated gases (P∼1–2 atm, T∼800–1600 K). The sensor is designed to achieve a high sensitivity to the temperature and a low sensitivity to cold boundary-layer effects and any changes in gas pressure or composition. The fixed-wavelength WMS-2f sensor is tested for temperature and CO₂ concentration measurements in a heated static cell (600–1200 K) and in non-reactive shock-tube experiments (900–1700 K) using CO₂–Ar mixtures. The relatively large CO₂ absorption strength near 2.7 μm and the use of a WMS-2f strategy minimizes noise and enables measurements with lower concentration, higher accuracy, better sensitivity and improved signal-to-noise ratio (SNR) relative to earlier work, using transitions in the 1.5 and 2.0 μm CO₂ combination bands. The standard deviation of the measured temperature histories behind reflected shock waves is less than 0.5%. The temperature sensor is also demonstrated in reactive shock-tube experiments of n-heptane oxidation. Seeding of relatively inert CO₂ in the initial fuel-oxidizer mixture is utilized to enable measurements of the pre-ignition temperature profiles. To our knowledge, this work represents the first application of wavelength modulation spectroscopy to this new class of diode lasers near 2.7 μm.     

Simultaneous measurement of liquid water film thickness and vapor temperature using near-infrared tunable diode laser spectroscopy

A fiber-based multiplexed tunable diode-laser absorption sensor with three near-infrared distributed-feedback diode lasers at ∼1.4 μm is used for simultaneous nonintrusive measurements of liquid water film thickness and vapor-phase temperature. Water film thicknesses are derived from broad-band absorption determined at two fixed wavelengths while gas-phase temperature above the film is obtained via two-line thermometry using the fast wavelength tuning with line-integrating absorption. Probing the liquid film at two wavelengths with significantly different liquid-phase absorption cross sections allows discriminating against additional signal losses due to surface fowling, reflection, and beam steering. The technique is demonstrated for liquid layers of defined thicknesses and in time-resolved measurements of evaporating films.     

Near- and mid-infrared laser-optical sensors for gas analysis

Semiconductor diode lasers were first developed in the mid-1960s and found immediate application as much needed tunable sources for high-resolution laser spectroscopy commonly referred to as tunable diode laser absorption spectroscopy (TDLAS). In this paper, currently available semiconductor lasers for spectroscopy in the near- and mid-infrared spectral region based upon gallium arsenide, indium phosphite, antimonides and lead-salt containing compounds will be reviewed together with the main features of TDLAS. Room-temperature measurements of atmospheric carbon dioxide near 2 μm will be discussed and recent results obtained with a fast chemical sensor for methane flux measurements based on lead-salt diode lasers operating near 7.8 μm will be presented.     

Application of a difference-frequency-mixing based diode-laser sensor for carbon monoxide detection in the 4.4–4.8 μm spectral region

An all-solid-state continuous-wave (cw) laser system for mid-infrared absorption measurements of the carbon monoxide (CO) molecule has been developed and demonstrated. The single-mode, tunable output of an external-cavity diode laser (ECDL) is difference-frequency mixed with the output of a 550-mW diode-pumped cw Nd:YAG laser in a periodically poled lithium niobate (PPLN) crystal to generate tunable cw radiation in the mid-infrared region. The wavelength of the 860-nm ECDL can be coarse tuned from 860.782 to 872.826 nm, allowing the sensor to be operated in the spectral region 4.4–4.8 μm. CO-concentration measurements were performed in CO/CO₂/N₂ mixtures in a room-temperature gas cell, in the exhaust stream of a well-stirred reactor (WSR) at Wright-Patterson Air Force Base and in a near-adiabatic hydrogen/air CO₂-doped flame. The noise equivalent detection limits were estimated to be 1.1 and 2.5 ppm per meter for the gas cell and flame experiments, respectively. These limits were computed for combustion gas at 1000 K and atmospheric pressure assuming a signal-to-noise ratio of 1. The sensor uncertainty was estimated to be 2% for the gas-cell measurements and 10% for the flame measurements based on the repeatability of the peak absorption. PACS 07.07.Df; 42.62.Fi; 42.65.Ky; 42.72.Ai     

Low-temperature performance of InP-based long-wavelength VCSELs

We have studied, for the first time, the parameters of long-wavelength InP-based buried tunnel junction (BTJ) VCSELs with substrate temperature varied in the range between 150 and 330 K. The BTJ-VCSELs with threshold currents <1 mA were designed by VERTILAS (Germany) to operate near 1512 nm and 1577 nm at room temperature (models VL-1512 and VL-1577, respectively). Reducing the substrate temperature of the lasers from room temperature to 150 K resulted in more than a fourfold increase of the threshold injection current accompanied with threefold and twofold increases in output power and slope efficiency, respectively. We have observed continuous single-mode tuning over intervals up to ∼20 nm (VL-1512) and ∼22 nm (VL-1577) at constant injection currents and substrate temperatures varied in a 180 K range. The emission wavelength was found to shift linearly with temperature with rates of 0.11 nm/K and 0.12 nm/K for lasers VL-1512 and VL-1577, respectively. The single-mode laser output reached ∼3 mW for both lasers cooled down to 173 K. Gas sensors based on BTJ-VCSELs can be temperature tuned over wide spectral intervals using either a cooler or a low ambient temperature to control laser substrate temperature. Ultra-sensitive gas concentration measurements under low ambient temperatures may include chemical analysis of the lower earth stratosphere and of the martian atmosphere. PACS 42.55.Px; 42.62.Fi; 39.30.+w     

Absorption measurements in dense cesium vapor using a UV–violet light-emitting diode

We present results of absorption measurements in a dense superheated cesium vapor generated in an all-sapphire cell using a UV–violet light-emitting diode as a continuum source. Due to the very effective thermal destruction of Cs₂ molecules, a number of diffuse and satellite bands appear around higher members of cesium principal series lines, which are not easily visible in saturated cesium vapor. From the temperature dependence of the diffuse features we can distinguish short-range singlet transitions from temperature-independent spectral features that stem either from a shallow lowest triplet state or from the long-range photo association spectra of triplet or singlet Cs₂ molecules. The limits of the present interpretation of the observed bands in the UV–violet spectral region are discussed. Received: 25 May 2000 / Revised version: 20 September 2000 / Published online: 13 December 2000     

Diode-laser-based sensor for ultraviolet absorption measurements of atomic mercury

A new sensor has been developed for measuring atomic mercury using absorption spectroscopy with 254-nm radiation generated from two sum-frequency-mixed diode lasers. Beams from a 375-nm external-cavity diode laser and a 784-nm distributed feedback diode laser are mixed in a beta-barium-borate crystal to generate approximately 4 nW of ultraviolet radiation. The development of the sensor is described along with extensive characterization experiments in a mercury vapor cell in the laboratory. An accuracy of ±6% in the absolute concentration of atomic mercury has been demonstrated by comparison with equilibrium vapor pressure calculations. The detection limit is approximately 0.1 parts per billion of atomic mercury in a meter path length for 300-K gas and a 10-s integration time. The insensitivity of the sensor to broadband attenuation is demonstrated. Measurements of collision-broadening coefficients for air, N₂, Ar, and CO₂ are reported, and implementation of wavelength-modulation spectroscopy with the sensor is demonstrated. Finally, results are presented from measurements with the sensor in situ in the exhaust stream of an actual coal-fired combustor. PACS 07.07.Df; 42.62.Fi; 42.65.Ky; 42.72.Bj     

Gas temperature measurements using widely tunable long-wavelength VCSEL

A method for gas temperature measurements with a widely tunable laser diode is presented. The method involves rapidly switching the laser frequency between two distantly spaced absorption lines chosen for optical thermometry. Direct absorption spectroscopy using a single-mode VCSEL was employed to probe the R10 and R22 lines of the 2ν₁+2ν₂ ⁰+ν₃ combination band of CO₂ near 6355.9 and 6363.7 cm^-1 sequentially. A specially designed 0.5-m cryogenic gas cell was filled with 10 mbar CO₂ at room temperature and cooled to 150 K with liquid N₂. The VCSEL was modulated with a 10-kHz ramp superimposed on a 1-kHz square waveform to scan two 0.04 cm^-1 intervals sequentially. The gas temperatures obtained with the VCSEL in the 150–300 K range are in a good agreement with those derived from gas pressure ratios. The maximum relative error of temperature measurements using the VCSEL was ± 3%. A compact VCSEL-based sensor can be developed for gas temperature and concentration measurements in the Martian atmosphere. The method proposed can be used for many applications including in situ monitoring of combustion processes. PACS 42.62.Fi; 42.55.Px; 39.30.+w     

Wavelength modulated cavity enhanced absorption spectroscopy of ammonia at 1994 nm

We describe the sensitive detection of ammonia by wavelength modulated cavity enhanced infrared tunable diode laser absorption spectroscopy at 1994 nm. The spectrometer can measure a fractional absorption of ∼10^-5 for an absorption pathlength of a few kilometers. The spectral resolution and sensitivity are sufficient to measure ammonia isotopomers (¹⁴NH₃, ¹⁵NH₃) in planetary atmospheres. The spectrometer is miniaturisable, so a future multiple-species version will be highly suitable for in situ planetary exploration and life-detection. PACS 42.62.Fi; 33.20.-t; 33.20.Ea     

Multi-mode absorption spectroscopy of oxygen for measurement of concentration, temperature and pressure

The use of multi-mode absorption spectroscopy (MUMAS) to detect multiple transitions in the A-band b¹Σ_g ⁺-X³Σ_g ^- of molecular oxygen is reported. The modelling of MUMAS signatures and the procedure for fitting such model signatures to experimental data obtained using a multi-mode diode laser is described. The technique is shown to allow accurate and precise measurement of concentration, temperature over the range 300 to 500 K and of pressure over the range 0.2 to 1 bar. Extension of the technique to other ranges of temperature and pressure and to other species is discussed. PACS 42.62.Fi; 33.20.Kf     

Application of quantum cascade lasers to trace gas analysis

Quantum cascade (QC) lasers are virtually ideal mid-infrared sources for trace gas monitoring. They can be fabricated to operate at any of a very wide range of wavelengths from ∼ 3 μm to ∼ 24 μm. Seizing the opportunity presented by mid-infrared QC lasers, several groups world-wide are actively applying them to trace gas sensing. Real world applications include environmental monitoring, industrial process control and biomedical diagnostics. In our laboratory we have explored the use of several methods for carrying out absorption spectroscopy with these sources, which include multipass absorption spectroscopy, cavity ring down spectroscopy (CRDS), integrated cavity output spectroscopy (ICOS), and quartz-enhanced photoacoustic spectroscopy (QEPAS). PACS 42.62.Fi; 42.62.Be; 07.88.+y; 33.20.Ea     

High spectral resolution analysis of tunable narrowband resonant grating waveguide structures

A high spectral resolution analysis of narrowband reflection filters based on resonant grating waveguide structures is presented. A tunable high-performance dye laser with ∼ 0.15 cm^-1 line width and a beam analyzing system consisting of three simultaneously controlled CCD cameras were used to investigate grating waveguide resonances at wavelengths in the 694 nm and 633 nm ranges. A reflectivity of ∼ 91% and a line width of ∼ 0.55 nm were measured and theoretically modeled for a resonant reflection filter specifically designed for the ruby laser wavelength 694.2 nm. For a second grating waveguide structure, designed for the helium-neon laser emission wavelength 632.8 nm, we observed a thermal shift of its spectral resonance position of several nanometers, when increasing the sample temperature by some degrees. An inverse thermal shift was observed when the structure was subsequently cooled down to room temperature. Our results suggest implementation of grating waveguide devices combining a narrow line width with a tunability of the resonant response into innovative concepts for reflection filter and sensor applications. PACS 42.62.-b; 42.79.Dj; 42.79.Gn