Tunable diode laser spectroscopy of benzene near 1684 nm with a low-temperature VCSEL

We describe the application of a long-wavelength vertical-cavity surface-emitting laser (VCSEL) with extended tuning range to the detection of benzene vapor at atmospheric pressure. A benzene absorption feature centered at 1684.24 nm was accessed by reducing the heat sink temperature of a VCSEL designed for room-temperature operation to −55°C. This allowed us to increase the injection current and thus to extend a single-scan tuning interval up to 46.4 cm⁻¹ or 13.2 nm around a central wavelength of 1687.4 nm. Five absorption lines of methane in the 5903–5950 cm⁻¹ range could be acquired within single laser scans at a repetition rate of 500 Hz. A benzene absorption feature between 5926 and 5948 cm⁻¹ was recorded for concentration measurements at atmospheric pressure using a single-pass 1.2 m absorption cell. A 50 ppmv mixture of CH₄ in N₂ was introduced into the cell along with benzene vapor to calibrate benzene concentration measurements. Benzene mixing ratios down to ∼90 ppmv were measured using a direct absorption technique. The minimum detectable absorbance and detection limit of benzene were estimated to be ∼10⁻⁴ and 30 ppmv, respectively. Using the wavelength modulation technique, we measured a second harmonic sensor response to benzene vapor absorption in air at atmospheric pressure as a function of modulation index. We conclude that a low-temperature monolithic VCSEL operating near 1684 nm can be employed in compact benzene sensors with a detection limit in the sub-ppm range.     

Telecom-grade fiber laser-based difference-frequency generation and ppb-level detection of benzene vapor in air around 3 μm

We report on the development of a field deployable compact laser instrument tunable over ∼232 cm⁻¹ from 3.16 to 3.41 μm (2932.5–3164.5 cm⁻¹) for chemical species monitoring at the ppb-level. The laser instrument is based on widely tunable continuous-wave difference-frequency generation (DFG), pumped by two telecom-grade fiber lasers. DFG power of ∼0.3 mW near 3.3 μm with a spectral purity of ∼3.3 MHz was achieved by using moderate pumping powers: 408 mW at 1062 nm and 636 mW at 1570 nm. Spectroscopic performance of the developed DFG-based instrument was evaluated with direct absorption spectra of ethylene at 3.23 μm (∼3094.31 cm⁻¹). Absorption spectra of vapor-phase benzene near 3.28 μm (∼3043.82 cm⁻¹) were recorded with Doppler-limited resolution. Line intensities of the most intense absorption lines of the ν ₁₂ band near 3043.8 cm⁻¹ were determined to support development of sensitive mid-infrared trace gas detection of benzene vapor in the atmosphere. Detection of benzene vapor in air at different concentration levels has been performed for the first time using multi-pass cell enhanced direct absorption spectroscopy at ∼3.28 μm with a minimum detectable concentration of 50 ppb (1σ).     

Analysis of trace impurities in semiconductor gas via cavity-enhanced direct frequency comb spectroscopy

Cavity-enhanced direct frequency comb spectroscopy (CE-DFCS) has demonstrated powerful potential for trace-gas detection based on its unique combination of high bandwidth, rapid data acquisition, high sensitivity, and high resolution, which is unavailable with conventional systems. However, previous demonstrations have been limited to proof-of-principle experiments or studies of fundamental laboratory science. Here, we present the development of CE-DFCS towards an industrial application—measuring impurities in arsine, an important process gas used in III–V semiconductor compound manufacturing. A strongly absorbing background gas with an extremely complex, congested, and broadband spectrum renders trace detection exceptionally difficult, but the capabilities of CE-DFCS overcome this challenge and make it possible to identify and quantify multiple spectral lines associated with water impurities. Further, frequency combs allow easy access to new spectral regions via efficient nonlinear optical processes. Here, we demonstrate detection of multiple potential impurities across 1.75–1.95 μm (5710–5130 cm⁻¹), with a single-channel detection sensitivity (simultaneously over 2000 channels) of ∼4×10⁻⁸ cm⁻¹ Hz^−1/2 in nitrogen and, specifically, an absorption sensitivity of ∼4×10⁻⁷ cm⁻¹ Hz^−1/2 for trace water doped in arsine.     

Sensitive detection of ammonia and ethylene with a pulsed quantum cascade laser using intra and interpulse spectroscopic techniques

Spectroscopic concentration measurements of ammonia and ethylene were done with a pulsed, distributed feedback (DFB) quantum cascade (QC) laser centered at 970 cm⁻¹. An astigmatic Herriot cell with 150 m path length was employed, and we compare the results from experiments using inter- and intrapulse techniques, respectively. The measurements include the detection of ammonia in breath with these methodologies. In the interpulse technique, the laser was excited with short current pulses (5–10 ns), and the pulse amplitude was modulated with an external current ramp resulting in a ∼0.3 cm⁻¹ frequency scan. A standard amplitude demodulation technique was implemented for extracting the absorption line, thus avoiding the need for a fast digitizer or a gated integrator. In the intrapulse technique, a linear frequency down-chirp is used for sweeping across the absorption line. A 200 ns long current pulse was used for these measurements which resulted in a spectral window of ∼1.74 cm⁻¹ during the down-chirp. The use of a room temperature mercury-cadmium-telluride detector resulted in a completely cryogen free spectrometer. We demonstrate detection limits of ∼3 ppb for ammonia and ∼5 ppb for ethylene with less than 10 s averaging time with the intrapulse method and ∼4 ppb for ammonia and ∼7 ppb for ethylene with the interpulse technique with an integration time of ∼5 s.     

QEPAS spectrophones: design, optimization, and performance

The impact of design parameters of a spectrophone for quartz-enhanced photoacoustic spectroscopy on its performance was investigated. The microresonator of spectrophone is optimized based on an experimental study. The results show that a 4.4 mm-long tube with 0.6 mm inner diameter yields the highest signal-to-noise ratio, which is ∼30 times higher than that of a bare QTF at gas pressures between 400 and 800 Torr. The optimized configuration demonstrates a normalized noise-equivalent absorption coefficient (1σ) of 3.3×10⁻⁹ cm⁻¹W/Hz^1/2 for C₂H₂ detection at atmospheric pressure. The effect of the changing carrier gas composition is studied. A side-by-side sensitivity comparison between QEPAS and conventional photoacoustic spectroscopy technique is reported.     

Oxygen measurements at high pressures with vertical cavity surface-emitting lasers

Measurements of oxygen concentration at high pressures (to 10.9 bar) were made using diode-laser absorption of oxygen A-band transitions near 760 nm. The wide current-tuning frequency range (>30 cm^-1) of vertical cavity surface-emitting lasers (VCSELs) was exploited to enable the first scanned-wavelength demonstration of diode-laser absorption at high pressures; this strategy is more robust than fixed-wavelength strategies, particularly in hostile environments. The wide tuning range and rapid frequency response of the current tuning were further exploited to demonstrate wavelength-modulation absorption spectroscopy in a high-pressure environment. The minimum detectable absorbance demonstrated, ∼1×10^-4, corresponds to ∼800 ppm-m oxygen detectivity at room temperature and is limited by etalon noise. The rapid- and wide-frequency tunability of VCSELs should significantly expand the application domain of absorption-based sensors limited in the past by the small current-tuning frequency range (typically <2 cm^-1) of conventional edge-emitting diode lasers. Received: 26 July 2000 / Revised version: 2 January 2001 / Published online: 20 April 2001     

CO2 isotope sensor using a broadband infrared source, a spectrally narrow 4.4 μm quantum cascade detector, and a Fourier spectrometer

We report a prototype CO₂ gas sensor based on a simple blackbody infrared source and a spectrally narrow quantum cascade detector (QCD). The detector absorption spectrum is centered at 2260 cm⁻¹ (4.4 μm) and has a full width at half maximum of 200 cm⁻¹ (25 meV). It covers strong absorption bands of two spectrally overlapping CO₂ isotopomers, namely the P-branch of ¹²CO₂ and the R-branch of ¹³CO₂. Acquisition of the spectral information and data treatment were performed in a Fourier transform infrared (FTIR) spectrometer. By flushing its sample compartment either with nitrogen, dry fresh air, ambient air, or human breath, we were able to determine CO₂ concentrations corresponding to the different gas mixtures. A detection limit of 500 ppb was obtained in these experiments.     

Application of 940 nm high-power DFB lasers for line-broadening measurements at normal pressure using a robust and compact setup

High-power distributed-feedback (DFB) lasers for the wavelength range near 940 nm (i.e. about 10,600 cm⁻¹) were used for line-broadening measurements of individual rotational-vibrational absorption lines of water vapour at atmospheric pressure using a minimalist set-up. The laser has a maximum output power larger than 500 mW. Over the whole power range from threshold to maximum power, it operates in single mode operation with a tuning range of 4.7 nm, i.e. 50 cm⁻¹, at 20°C. With an emission line-width ≤2 MHz (0.66×10⁻⁴ cm⁻¹), the device is well suited for high-resolution spectroscopy.     

Spectral components that form UV absorption spectrum of Ce3+ and Ce(IV) valence states in matrix of photothermorefractive glasses

We have measured the UV absorption spectra of photothermorefractive glasses of the system Na₂O-ZnO-Al₂O₃-NaF-SiO₂ doped by cerium oxide in the range of (2.8–5.0) × 10⁴ cm⁻¹ (360–200 nm). The spectra have been processed by the method of dispersion analysis based on the analytical convolution model for the complex dielectric function of glasses. We show that the absorption band centered at 3.3 × 10⁴ cm⁻¹ (∼303 nm) that is attributed to the transition 2F _5/2 → 5d in the Ce³⁺ ion, is an envelope of three spectral components. The broad absorption range (3.5–4.7) × 10⁴ cm⁻¹ (200–270 nm) that is commonly interpreted as a charge transfer band of the Ce(IV) valence state, is an envelope of at least three spectral components.     

Detection of <Emphasis Type="Italic">trans</Emphasis>-isomers of hydrocarbon residues of lipid molecules by IR absorption

IR spectroscopy is used for a comparative analysis of the trans-isomerization of double bonds in hydrocarbon residuals of lactic and hydrogenated lipids. The maximum of the absorption band of the trans-isomers for all the lipid samples is found to lie at 965 cm⁻¹. An absorption band at 970 cm⁻¹ is discovered in the spectra of the lactic lipids near the analytic band of the trans-isomers at 965 cm⁻¹. Based on a gaussian approximation for their absorption spectral bands, the trans-isomer content in the lactic lipid samples is 10–11%. The absorption by lipid molecules at 970 cm⁻¹ has to be taken into account when determining the trans-isomer content of fat and oil products. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 138–142, January–February, 2009.     

Miniaturized resonant photoacoustic cell of inclined geometry for trace-gas detection

A photoacoustic cell intended for laser detection of trace gases is represented. The cell is adapted so as to enhance the gas-detection performance and, simultaneously, to reduce the cell size. The cell design provides an efficient cancellation of the window background (a parasite response due to absorption of laser beam in the cell windows) and acoustic isolation from the environment for an acoustic resonance of the cell. The useful photoacoustic response from a detected gas, window background and noise are analyzed in demonstration experiments as functions of the modulation frequency for a prototype photoacoustic cell with the internal volume ∼0.6 cm³. The minimal detectable absorption for the prototype is estimated to be ∼1.2×10⁻⁸ cm⁻¹ W Hz^−1/2.     

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.     

Light-emitting Si nanostructures formed in silica layers by irradiation with swift heavy ions

Thin SiO₂ layers were implanted with 140 keV Si ions to a dose of 10¹⁷ cm⁻². The samples were irradiated with 130 Mev Xe ions in the dose range of 3×10¹²–10¹⁴ cm⁻², either directly after implantation or after pre-annealing to form the embedded Si nanocrystals. In the as-implanted layers HREM revealed after Xe irradiations the 3–4 nm-size dark spots, whose number and size grew with increase in Xe dose. A photoluminescence band at 660–680 nm was observed in the layers with the intensity dependent on the Xe dose. It was found that passivation with hydrogen quenched that band and promoted emission at ∼780 nm, typical of Si nanocrystals. In spectra of pre-annealed layers strong ∼780 nm peak was observed initially. Under Xe bombardment its intensity fell, with subsequent appearance and growth of 660–680 nm band. The obtained results are interpreted as the emission at ∼660–680 nm belonging to the imperfect Si nanocrystals. It is concluded that electronic losses of Xe ions are mainly responsible for formation of new Si nanostructures in ion tracks, whereas elastic losses mainly introduce radiation defects, which quench the luminescence. Changes in the spectra with growth of Xe ion dose are accounted for by the difference in the diameters of Xe ion tracks and their displacement cascades.     

Nonlinear optical absorption and refraction in Ru, Pd, and Au nanoparticle suspensions

We present the results of studies of the nonlinear optical properties of Pd, Ru, and Au nanoparticles. We studied the nonlinear refraction and nonlinear absorption of suspensions of these nanoparticles at 1064-nm wavelength. A relatively strong nonlinear absorption of the Pd nanoparticles was observed in the case of 1064-nm, 50-ps pulses (β=2×10⁻⁹ m W⁻¹). The Ru and Pd nanoparticles showed weak negative nonlinear refraction (γ∼−(6–8)×10⁻¹⁶ m² W⁻¹) in this spectral range. In the case of the Au nanoparticles, a saturated absorption at 532 nm dominated over other nonlinear optical processes.     

Wavelength modulation and cavity enhanced absorption spectroscopy using ～1.9?μm radiation produced by difference frequency generation with a MgO doped PPLN crystal

We have demonstrated the production of ∼1.9 μm near-infrared radiation by using difference frequency generation within a 5% MgO doped PPLN crystal by coupling ∼735 nm radiation from a tunable external cavity diode laser with relatively high powered 532 nm radiation from both Nd:YVO₃ and Nd:YAG lasers. The radiation produced is of low power, ∼15 μW, and was used in conjunction with the sensitivity enhancing techniques of wavelength modulation spectroscopy (WMS) and cavity enhanced absorption spectroscopy (CEAS). Experiments were carried out on rotationally resolved transitions in the combination bands of NH₃ and CO₂ in the 1.9 μm region. An α _min value of 3.6×10⁻⁶ cm⁻¹ Hz^−1/2 was achieved for WMS measurements on CO₂. A comparable α _min value of 2.2×10⁻⁶ cm⁻¹ Hz^−1/2 was achieved for NH₃ using CEAS. The low NIR power indicates that despite the level of MgO doping quoted for the crystal, under prolonged exposure photorefractive damage has occurred.     

Influence of post-grown Li-rich and Li-poor vapor transport equilibration on composition, OH− absorption and optical-damage threshold of Mg (5 mol%) : LiNbO3 crystals

Li-rich (Li-poor) vapor transport equilibration (VTE) treatments on a number of Z-cut 0.47 mm thick congruent MgO (5 mol% in melt) : LiNbO₃ crystals were carried out at 1100°C over different durations ranging in 1–172 (40–395) h. Neutron activation analysis shows that neither Li-rich nor Li-poor VTE-induced Mg and Nb loss from the crystal occurred. The Li₂O content in the crystal was measured as a function of VTE duration by the gravimetric method. The Li-rich/Li-poor VTE effects on OH⁻ absorption were studied in comparison with the as-grown crystal. The study shows that the Li-rich VTE results in OH⁻ absorption band annihilation. After further oxidation treatment the band reemerges and peaks at the same wavenumber as that of the as-grown crystal (∼3535.6 cm⁻¹), showing that the MgO concentration in the Li-rich VTE crystal is still above the optical-damage threshold. The Li-poor VTE causes OH⁻ band shift to 3486.3–3491.6 cm⁻¹, indicating that the MgO concentration in all Li-poor VTE crystals is all below the optical-damage threshold. Further successive Li-rich VTE and oxidation treatments on the Li-poor VTE-treated crystal lead the band to shift back to 3535.6 cm⁻¹, showing that the post Li-rich VTE brought the Li-poor VTE-treated crystal above the optical-damage threshold again. It is found that the peaking position, band width, peaking absorption and band area of the absorption at ∼3486 cm⁻¹ all increase monotonously with the decrease of the Li₂O content arising from prolonged Li-poor VTE, and quantitative relationships to the Li₂O content are established for the latter two parameters. The VTE effects on the OH⁻ absorption are conducted with the VTE-induced OH⁻ content alteration and charge redistribution.     

Nanosecond laser-induced surface damage of optical multimode fibers and their preforms

High-power optical multimode fibers are essential components for materials processing and surgery and can limit the performance of expensive systems due to breakdown at the end faces. The aim of this paper is the determination of laser-induced damage thresholds (LIDT) of fibers (FiberTech) and preforms (Heraeus Suprasil F300). Preforms served as models. They were heated up to maximum temperatures of 1100, 1300 and 1500°C and cooled down to room temperature at rates of 10 K min⁻¹ (oven) and ∼10⁵ K min⁻¹ (quenched in air) to freeze in various structural states simulating different conditions similar to a drawing process during the production of fibers. Single- and multi-pulse LIDT measurements were done in accordance with the relevant ISO standards. Nd:YAG laser pulses with durations of 15 ns (1064 nm wavelength) and 8.5 ns (532 nm) at a repetition rate of 10 Hz were used. For the preforms, LIDT values (1-on-1) ranged from 220 to 350 J/cm² (1064 nm) and from 80 to 110 J/cm² (532 nm), respectively. A multi-pulse impact changed the thresholds to lower values. The LIDT (1064 nm wavelength) of the preforms can be regarded as a lower limit for those of the fibers.     

Mid-infrared upconversion spectroscopy based on a Yb:fiber femtosecond laser

We present a system for molecular spectroscopy using a broadband mid-infrared laser with near-infrared detection. Difference frequency generation of a Yb:fiber femtosecond laser produced a mid-infrared (MIR) source tunable from 2100–3700 cm⁻¹ (2.7–4.7 μm) with average power up to 40 mW. The MIR spectrum was upconverted to near-infrared wavelengths for broadband detection using a two-dimensional dispersion imaging technique. Absorption measurements were performed over bandwidths of 240 cm⁻¹ (7.2 THz) with 0.048 cm⁻¹ (1.4 GHz) resolution, and absolute frequency scale uncertainty was better than 0.005 cm⁻¹ (150 MHz). The minimum detectable absorption coefficient per spectral element was determined to be 4.4×10⁻⁷ cm⁻¹ from measurements in low pressure CH₄, leading to a projected detection limit of 2 parts-per-billion of methane in pure nitrogen. In a natural atmospheric sample, the methane detection limit was found to be 30 parts-per-billion. The spectral range, resolution, and frequency accuracy of this system show promise for determination of trace concentrations in gas mixtures containing both narrow and broad overlapping spectral features, and we demonstrate this in measurements of air and solvent samples.     

High-speed vertical-cavity surface-emitting laser (VCSEL) absorption spectroscopy of ammonia (NH<Subscript>3</Subscript>) near 1.54 μm

A single-frequency VCSEL has been used for the first time for high-resolution spectroscopy near 1.5 μm. The incorporated buried-tunnel-junction technology enabled the realization of a long-wavelength InGaAlAs/InP VCSEL with low threshold current (0.925 mA), high output powers (0.576 mW) and low series resistance (60 Ω). The high-speed tuning capability of the long-wavelength VCSEL was investigated and used to conduct high-speed absorption spectroscopy. The peak tuning speed was measured to be 3.4 cm^-1/μs and a 4.5-cm^-1-wide NH₃ spectrum was recorded in 2 μs. The VCSEL was used to measure highly resolved low-pressure spectra for pressures ranging from 9.6 mbar to 1 bar. The measured Doppler-broadened linewidth of 0.02 cm^-1 agrees within 3% with the theoretical calculations. The availability and various advantages of 1.3–2-μm single-frequency VCSELs as compared to edge-emitting diode lasers, such as a large current tuning range even at very high tuning frequencies, and low production costs, should significantly expand the application fields for near-infrared laser gas sensors. Received: 17 July 2002 / Revised version: 4 December 2002 / Published online: 12 May 2003 RID="*" ID="*"Corresponding author. Fax: +43-1/58801-15999, E-mail: Gerhard@Totschnig.com     

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