Flexible laser diode trace gas sensor based on cavity ringdown spectroscopy with an optical fiber-coupled high-finesse external-cavity diode laser

A flexible and portable trace nitrogen dioxide sensor based on cavity ringdown spectroscopy using an optical fiber-coupled high-finesse cavity was successfully demonstrated. Tailoring the spatial mode matching condition of the core of an optical fiber and high-finesse external cavity allows for effective optical feedback into an antireflection-coated laser diode for stable resonant enhancement of the external cavity. The external cavity, which works as a ringdown cavity, could be remotely located from the light source and receiver section by only a single mode optical fiber. The sensitivity was found to be 1.0×10⁻⁷ cm⁻¹ in a compact 1-cm³ ringdown cavity volume.     

Self-mixing interference effects in tunable diode laser absorption spectroscopy

We report the effects of self-mixing interference on gas detection using tunable diode laser spectroscopy. For very weak feedback, the laser diode output intensity gains a sinusoidal modulation analogous to that caused by low finesse etalons in the optical path. Our experiments show that self-mixing interference can arise from both specular reflections (e.g. cell windows) and diffuse reflections (e.g. Spectralon^™ and retroreflective tape), potentially in a wider range of circumstances than etalon-induced interference. The form and magnitude of the modulation is shown to agree with theory. We have quantified the effect of these spurious signals on methane detection using wavelength modulation spectroscopy and discuss the implications for real gas detectors.     

Performance evaluation of a near infrared QEPAS based ethylene sensor

A sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) was evaluated for the detection of trace levels of ethylene at atmospheric pressure using a fiber coupled DFB diode laser emitting in the 1.62 μm spectral range. A noise-equivalent QEPAS signal of ∼4 ppm C₂H₄ was achieved for a 0.7 s data acquisition time using wavelength-modulation with a second-harmonic detection scheme on the strongest C₂H₄ absorption peak at 6177.14 cm⁻¹ with an average optical power of ∼15 mW. Improved detection sensitivity of 0.5 and 0.3 ppm C₂H₄ (1σ) was demonstrated using longer averaging time of 70 and 700 s, respectively. Important characteristics for the QEPAS based sensor operation in real-world conditions are presented, particularly the influence of external temperature variations. Furthermore, the response time of the ethylene sensor was measured in different configurations and it is shown that the QEPAS technique can provide a response time in a few seconds range even without active gas flow.     

Methods for controlling of the laser-induced absorption in a BTO crystal by using of cw-laser radiation

The iron-atom concentration distribution as well as the gas-phase temperature was measured via laser-induced fluorescence (LIF) during iron-oxide nanoparticle synthesis in a low-pressure hydrogen/oxygen/argon flame reactor using ironpentacarbonyl (Fe(CO)₅) as precursor. Temperature measurements based on multi-line NO-LIF imaging are used to correct for temperature-dependent ground-state populations. The concentration measurement is calibrated based on line-of-sight absorption measurements. The influence of the precursor on the flame is observed at precursor concentrations larger than 70 ppm as the flame front moves closer to the burner surface with increasing Fe(CO)₅ concentration.     

Frequency stabilization of CO laser using RF optogalvanic Lamb-dip

The Lamb dip of CO rovibrational transition is detected by a room temperature extracavity RF optogalvanic cell and employed to stabilize the frequency of a CO laser. The S/N ratio of optogalvanic signal is about 2000  at optical power < 1 W. The relative depth of Lamb dip is 2.3%. The S/N ratios of first and third harmonic demodulated saturation signals are about 40  and 10  , respectively. The CO laser is stabilized using the first harmonic demodulated signal, and the frequency stability is better than 300 kHz. Concurrently, the influences of operational parameters, which include the coil current, partial pressures of gas mixture, are investigated. A simple model for the influence of coil current is presented, and further improvements are addressed as well.     

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.     

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.     

Development of an optical parametric generator with pulsed dye amplification for high-resolution laser spectroscopy

An injection-seeded optical parametric generator (OPG), coupled with three pulsed dye amplification (PDA) stages, was shown to produce tunable, narrow linewidth laser radiation. The OPG was composed of a pair of beta barium borate (β-BBO) crystals and pumped by the third harmonic (355 nm) output of a seeded Nd:YAG laser. The OPG was injection-seeded at the idler wavelength (824 nm) using an external cavity diode laser (ECDL) with a mode-hop-free tuning range of 20 GHz. Using the PDA stages, the OPG output signal (624 nm) was amplified to 19 mJ/pulse, while maintaining a spectral linewidth of approximately 160 MHz at full-width-half-maximum (FWHM) which was within a factor of 2 of the Fourier limit. A system of lenses and apertures was used to minimize amplified spontaneous emission (ASE) in the PDA stages. Using the OPG/PDA system, two-photon laser-induced fluorescence measurements of atomic oxygen were performed by sum-frequency-mixing the 624-nm beam with the third harmonic output of the seeded Nd:YAG laser to generate approximately 1 mJ/pulse of ultraviolet radiation near 226 nm. Voigt line shapes were found to be in good agreement with oxygen atom spectra in atmospheric-pressure, laminar, counter-flow flames; the magnitude of Doppler and collisional broadening was approximately the same. The measured O-atom concentration profile was found to compare well with that calculated using an opposed-flow flame code.     

Investigation of heavy-metal accumulation in selected plant samples using laser induced breakdown spectroscopy and laser ablation inductively coupled plasma mass spectrometry

Single-pulse Laser-Induced Breakdown Spectroscopy (LIBS) and Laser-Ablation Inductively Coupled Plasma Mass-Spectrometry (LA-ICP-MS) were applied for mapping the silver and copper distribution in Helianthus Annuus L. samples treated with contaminant in controlled conditions. For Ag and Cu detection the 328.07 nm Ag(I) and 324.75 nm Cu(I) lines were used, respectively. The LIBS experimental conditions (mainly the laser energy and the observation window) were optimized in order to avoid self-absorption effect in the measured spectra. In the LA-ICP-MS analysis the Ag 107 and Cu 63 isotopes were detected. The capability of these two analytical techniques for high-resolution mapping of selected trace chemical elements was demonstrated.     

Spectroscopic trace-gas sensor with rapidly scanned wavelengths of a pulsed quantum cascade laser for in situ NO monitoring of industrial exhaust systems

Development of a pulsed quantum cascade laser (QCL)-based spectroscopic trace-gas sensor for sub-part-per-million detection of nitric oxide (NO) and capable of monitoring other molecular species such as CO₂, H₂O, and NH₃ in industrial combustion exhaust systems is reported. Rapid frequency modulation is applied to the QCL to minimize the influence of fluctuating non-selective absorption. A novel method utilizes only a few laser pulses within a single wavelength scan to probe an absorption spectrum at precisely selected optical frequencies. A high-temperature gas cell was used for laboratory evaluation of the NO sensor performance. A noise-equivalent sensitivity (1) of 100 ppb × m/ at room temperature and 200 ppb × m/ at 630 K was achieved by measuring the NO R(6.5) absorption doublet at 1900.075 cm^–1.     

Development of a compact CO2 sensor based on near-infrared laser technology for enological applications

This paper reports the development of an infrared laser spectrometer using commercial diode laser emitting at 2.68 μm. The instrument is designed to measure CO₂ concentrations above a glass poured with a sparkling liquid, such as beer or champagne in the present case. This spectrometer was developed in order to realize the cartography of CO₂ outgassing in the headspace above various glasses. We provide details of the instrument design and data processing. Absorption lines were carefully selected to minimize interferences from neighboring water vapor transitions. The instrument performance allows to measure ambient CO₂ concentrations so that one can be very confident in the CO₂ concentrations measurements above the glass. Some preliminary results on sparkling liquids such as beer and champagne are presented and compared to a model describing the flux of CO₂ discharging from glasses due to the contribution of bubbles.     

Signal-to-noise enhancement techniques for quantum cascade absorption spectrometers employing optimal filtering and other approaches

Optical feedback to the laser source in tunable diode laser spectroscopy (TDLS) is known to create intensity modulation noise due to elatoning and optical feedback (i.e. multiplicative technical noise) that usually limits spectral signal-to-noise (S/N). The large technical noise often limits absorption spectroscopy to noise floors 100-fold greater than the Poisson shot noise limit due to fluctuations in the laser intensity. The high output powers generated from quantum cascade (QC) lasers, along with their high gain, makes these injection laser systems especially susceptible to technical noise. In this article we discuss a method of using optimal filtering to reduce technical noise. We have observed S/N enhancements ranging from ∼20% to a factor of ∼50. The degree to which optimal filtering enhances S/N depends on the similarity between the Fourier components of the technical noise and those of the signal, with lower S/N enhancements observed for more similar Fourier decompositions of the signal and technical noise. We also examine the linearity of optimal filtered spectra in both time and intensity. This was accomplished by creating a synthetic spectrum for the species being studied (CH₄, N₂O, CO₂ and H₂O in ambient air) utilizing line positions and linewidths with an assumed Voigt profile from a commercial database (HITRAN). Agreement better than 0.036% in wavenumber and 1.64% in intensity (up to a 260-fold intensity ratio employed) was observed. Our results suggest that rapid ex post facto digital optimal filtering can be used to enhance S/N for routine trace gas detection. Received: 1 April 2002 / Revised version: 7 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-509/376-6066, E-mail: robert.disselkamp@pnl.gov     

Line strength and collisional broadening studies of hydrogen sulphide in the 1.58 μm region using diode laser spectroscopy

High resolution diode laser spectroscopy has been applied to the detection of hydrogen sulphide at ppm levels utilizing different transitions within the region of the ν ₁+ν ₂+ν ₃ and 2ν ₁+ν ₂ combination bands around 1.58 μm. Suitable lines in this spectral region have been identified, and absolute absorption cross sections have been determined through single-pass absorption spectroscopy and confirmed in the Doppler linewidth regime using cavity enhanced absorption spectroscopy (CEAS). The desire for a sensitive system potentially applicable to H₂S sensing at atmospheric pressure has led to an investigation on suitable transitions using wavelength modulation spectroscopy (WMS). The set-up sensitivity has been calculated as 1.73×10⁻⁸ cm⁻¹ s^1/2, and probing the strongest line at 1576.29 nm a minimum detectable concentration of 700 ppb under atmospheric conditions has been achieved. Furthermore, pressure broadening coefficients for a variety of buffer gasses have been measured and correlated to the intermolecular potentials governing the collision process; the H₂S–H₂S dimer well depth is estimated to be 7.06±0.09 kJ mol⁻¹.     

Local crystallization in an oxyfluoride glass doped with Er3+ ions using a continuous argon laser

Local crystalline formation in erbium doped oxyfluoride glass has been obtained under a cw Argon laser irradiation up to 1.8 W pumping power. By exciting at 514 nm, the emission from 800 nm and 850 nm corresponding to the ⁴S_3/2(²H_11/2)→⁴I_13/2 electronic transitions have been analyzed both inside and outside the irradiated area. The changes in the emission spectra indicate that the high power Ar laser irradiation has resulted in a localized desvitrification process. The temperature dependence of the fluorescence intensity ratio of the 800 nm and 850 nm emission bands has been used to determine the temperature of the irradiated zone. Moreover, the average lifetime of the ⁴S_3/2(²H_11/2) thermalized levels have been measured as a function of the excitation spot position. An important decrease is observed at the irradiated area. These results confirm that a localized cristalline phase has been created by the laser action.     

Sensitive detection of methane and nitrous oxide isotopomers using a continuous wave quantum cascade laser

A continuous wave quantum cascade laser (QCL), operating near 8.1 μm, was used for wavelength modulation spectroscopy of methane (CH₄) and nitrous oxide (N₂O) stable isotopes. Several rotational transitions of ¹⁴N₂ ¹⁶O, ¹⁵N¹⁴N¹⁶O, ¹⁴N₂ ¹⁸O, ¹⁴N₂ ¹⁷O, ¹³CH₄ and ¹²CH₄ fundamental bands were detected. The noise-equivalent absorbance was measured to be less than 10^-5 in a 1-Hz bandwidth. A characterization of the laser source was also performed. The use of a QCL spectrometer for high-precision isotope ratio measurements is discussed. Received 14 March 2002     

Rapidly swept, continuous-wave cavity ringdown spectroscopy with optical heterodyne detection: single- and multi-wavelength sensing of gases

Spectroscopic sensing of gases can be performed with high sensitivity and photometric precision by cavity ringdown (CRD) absorption spectroscopy. Our cavity ringdown spectrometer incorporates continuous-wave (cw) tunable diode lasers, fibre-optic coupling and standard photonics and optical telecommunications components. It comprises a rapidly swept optical cavity in a single-ended optical heterodyne transmitter–receiver configuration, enabling optical absorption of gases to be recorded either as single-frequency scanned spectra or as simultaneous, multi-wavelength tailored spectra. By measuring weak near-infrared rovibrational spectra of carbon dioxide gas (CO₂), with high resolution in the vicinity of 1.53 μm, we have realised a noise-limited absorption sensitivity of 2.5×10^-9 cm^-1 Hz^-1/2. Analytical sensitivity limits (both actual and projected) and prospective gas-diagnostic applications are discussed. Our approach to cw-CRD spectroscopy offers high performance in a relatively simple, low-cost, compact instrument that is amenable to chemical analysis of trace gases in medical, agricultural, industrial and environmental situations. Received: 16 May 2002 / Revised version: 3 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +61-2/9850-8313, E-mail: brian.orr@mq.edu.au     

Near- and mid-infrared laser radiation interaction with eye tissue

Comparison of the eye tissue transmission for laser radiations with the wavelengths 0.75, 1.08, 1.34, 1.44, 1.54, 1.66, 2.01, 2.69, and 2.94 μm was made with the aim to understand the possible tissue injury by the particular light. From the step by step transmission measurements of the various human eye tissues (in vitro) it was recognized that the value of the transmitted energy in particular segments is different for various wavelengths yielding substantial fluence differences on the retina and anterior segments, mainly.     

3.5-μm high-resolution gas sensing employing a LiNbO3 QPM-DFG waveguide module

Diode laser technology coupled with a wavelength-conversion unit to produce mid-infrared narrow bandwidth laser light applicable to trace-gas detection and with the potential for high-resolution spectroscopy is described. Quasi-phase-matched difference-frequency generation (QPM-DFG) in a compact and fibre-coupled periodically poled lithium niobate (PPLN) waveguide module mixing 1063 and 1525-nm radiations has been adopted for generating 34 μW of 3.5-μm wavelength laser light. Optical detection methods, including sensitive wavelength modulation spectroscopy and a rapid wavelength chirp technique, have been employed with a single-pass cell to investigate methane and formaldehyde absorption profiles around 2855 cm⁻¹, as proof of principle experiments for high sensitivity and resolution spectroscopy on atmospherically important molecules.     

Optodynamic monitoring of laser micro-drilling of glass by using a laser probe

We present a new method for monitoring of the laser micro-drilling process. The method is based on detection of acoustic waves in air above the processed sample using a laser beam deflection probe (LBDP). We present an augmentation of the experimental set-up by means of a digital micrographic system which enables the acquisition of images of the plasma plume and of the hole cross-section during a drilling sequence. Comparing the acquired images with the detected LBDP signals, we examine the drilling process from a new perspective.     

Ultrashort laser ablation of PMMA and intraocular lenses

The use of intraocular lenses (IOLs) is the most promising method to restore vision after cataract surgery. Several new materials, techniques, and patterns have been studied for forming and etching IOLs to improve their optical properties and reduce diffractive aberrations. This study is aimed at investigating the use of ultrashort laser pulses to ablate the surface of PMMA and intraocular lenses, and thus provide an alternative to conventional techniques. Ablation experiments were conducted using various polymer substrates (PMMA samples, hydrophobic acrylic IOL, yellow azo dye doped IOL, and hydrophilic acrylic IOL consist of 25% H₂O). The irradiation was performed using 100 fs pulses of 800 nm radiation from a regeneratively amplified Ti:sapphire laser system. We investigated the ablation efficiency and the phenomenology of the ablated patterns by probing the ablation depth using a profilometer. The surface modification was examined using a high resolution optical microscope (IOLs) or atomic force microscope—AFM (PMMA samples). It was found that different polymers exhibited different ablation characteristics, a result that we attribute to the differing optical properties of the materials. In particular, it was observed that the topography of the ablation tracks created on the hydrophilic intraocular lenses was smoother in comparison to those created on the PMMA and hydrophobic lens. The yellow doped hydrophobic intraocular lenses show higher ablation efficiency than undoped hydrophobic acrylic lenses.