Rapid and sensitive trace gas detection with continuous wave Optical Parametric Oscillator-based Wavelength Modulation Spectroscopy

A fiber-amplified Distributed Bragg Reflector diode laser is used to pump a continuous wave, singly resonant Optical Parametric Oscillator (OPO). The output radiation covers the 3–4 μm with ability of rapid (100 THz/s) and broad mode-hop-free tuning (5 cm⁻¹). Wavelength Modulation Spectroscopy is combined with the OPO to take optimal advantage of the spectral scan speed. The sensitivity of the system was determined as 0.8 ppbv (parts-per-billion by volume) for ethane (C₂H₆) for the absorption peak at 2996.9 cm⁻¹ recorded in 1.3 seconds, corresponding to a noise equivalent absorption sensitivity (NEAS) of 1.2×10⁻⁹ cm⁻¹/Hz^1/2. A comparison between results using the 1^st, 2^nd and 4^th harmonic derivative signal from wavelength modulation was performed. The broad continuous tunability was demonstrated by covering 35 cm⁻¹ while recording absorption features of ethane, methane and water.     

A tunable diode-laser spectrometer for the MIR region near 7.2 μm applying difference-frequency generation in AgGaSe2

2 and two diode lasers as pump sources are presented. A single-mode Fabry–Pérot-type tunable diode laser (TDL) and an external-cavity diode laser (ECL) were combined to generate radiation in the mid-infrared region near 7.2 μm. With a TDL at a wavelength of approximately 1290 nm and an ECL emitting between 1504 and 1589 nm it was possible to carry out spectroscopic experiments concerning SO₂ at five different phasematching points between 1350 and 1400 cm^-1 by fixing the wavelength of one pump laser and tuning the wavelength of the other. With an input power of 8 mW for the single-mode Fabry–Pérot-type diode laser and 6 mW for the external-cavity laser an output power of about 10 nW was generated. Using the tuning capabilities of the external-cavity laser a spectral region up to 5 cm^-1 could be covered within one scan. Measurements of SO₂ absorption lines at low pressure demonstrate the high-resolution features of the spectrometer. Moreover, these data provide new direct experimental phasematching data for the rarely investigated spectral region at 7.2 μm. Received: 27 October 1997/Revised version: 8 May 1998     

Broadly tunable difference-frequency spectrometer for trace gas detection with noncollinear critical phase-matching in LiNbO3

3 is reported. Using an external cavity diode laser, tunable from 795 to 825 nm, and a cw diode-pumped Nd:YAG ring laser at 1064 nm, we produced narrowband mid-ir laser light between 3.16 and 3.67 μm. This broad tuning range of 440 cm^-1 can be critically phase-matched by changing the external crystal angle within a range of only 0.4°. Even for a fixed crystal angle broadband phase-matching over 230 cm^-1 was achieved. No realignment was required when tuning the laser over the whole wavelength range, which enabled the use of a compact 36-m multipass cell as gas chamber. The conversion efficiency could be improved by almost a factor of 3 by applying noncollinear instead of collinear phase-matching, resulting in 30 nW of idler power with good beam quality. Spectra of methane were recorded in laboratory air, which demonstrate the rapid and continuous broad tunability at high sensitivity, enabling sub-ppm detection. Finally, wavelength modulation spectroscopy at high resolution was applied as a promising tool for further inproving the performance of this laser spectrometer. Received: 16 March 1998/Revised version: 1 July 1998     

Automatically tunable continuous-wave optical parametric oscillator for high-resolution spectroscopy and sensitive trace-gas detection

We present a high-power (2.75 W), broadly tunable (2.75–3.83 μm) continuous-wave optical parametric oscillator based on MgO-doped periodically poled lithium niobate. Automated tuning of the pump laser, etalon and crystal temperature results in a continuous wavelength coverage up to 450 cm^-1 per poling period at <5×10^-4 cm^-1 resolution. The versatility of the optical parametric oscillator as a coherent light source in trace-gas detection is demonstrated with photoacoustic and cavity ring-down spectroscopy. A 17-cm^-1-wide CO₂ spectrum at 2.8 μm and multi-component gas mixtures of methane, ethane and water in human breath were measured using photoacoustics. Methane (at 3.2 μm) and ethane (at 3.3 μm) were detected using cavity ring-down spectroscopy with detection limits of 0.16 and 0.07 parts per billion by volume, respectively. A recording of ¹²CH₄ and ¹³CH₄ isotopes of methane shows the ability to detect both species simultaneously at similar sensitivities. PACS 42.65.Yj; 42.72.Ai; 42.62.Fi     

Compact sensor for methane detection in the mid infrared region based on Quartz Enhanced Photoacoustic Spectroscopy

A compact system for methane sensing based on the Quartz-Enhanced Photoacoustic Spectroscopy technique has been developed. This development has been taken through two versions which were based respectively on a Fabry Perot quantum wells diode laser emitting at 2.3 μm, and on a quantum wells distributed feedback diode laser emitting at 3.26 μm. These lasers emit near room temperature in the continuous wave regime. A spectrophone consisting of a quartz tuning fork and one steel microresonator was used. Second derivative wavelength modulation detection was used to perform low methane concentration measurements. The sensitivity and the linearity of the QEPAS sensor were studied. A normalized noise equivalent absorption coefficient of 7.26 × 10⁻⁶ cm⁻¹ W/Hz^1/2 was achieved. This corresponds to a detection limit of 15 ppmv for 12 s acquisition time.     

Wide single-mode tuning of a 3.0- 3.8-mum, 700-mW, continuous-wave Nd:YAG-pumped optical parametric oscillator based on periodically poled lithium niobate

A new optical parametric oscillator (OPO) for the mid-infrared wavelength region of 3-3.8mum with an idler output power of up to 1.5 W has been developed. The singly resonant OPO is pumped by a single-mode, 10-W, continuous-wave Nd:YAG laser and consists of a bow-tie ring cavity with a fan-out periodically poled lithium niobate crystal and a low-finesse intracavity air-spaced etalon. The single-frequency idler output can be continuously tuned over 24 GHz with 700-mW power by tuning of the pump laser. The tuning was demonstrated by recording of an absorption line of ethane with photoacoustic spectroscopy.     

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

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

A cw AgGaS2 difference frequency spectrometer with diode lasers as pump sources

2 and two diode lasers as pump sources and experiments with this setup are presented. In contrast to the majority of known applications of the difference frequency mixing with solid state or gas lasers, we apply two single mode diode lasers with emission wavelengths of 690 nm and 805 nm, respectively. By fixing the emission wavelength of one diode laser and tuning the wavelength of the second laser, by changing temperature or excitation current, we can cover typically 0.87 cm^-1 (FWHM) in good agreement with recently published data and theory. With an input power of 20 mW and 6 mW we achieved an output power in the nW-range. To demonstrate the capabilities of the spectrometer we scanned CO and OCS absorption lines near 2107 cm^-1. From these experiments we deduce an overall signal-to-noise ratio of 1000:1 and a spectral resolution better than 30 MHz. With such parameters a trace gas detection of CO at sub-ppm level will be possible. Received: 19 August 1996/Revised version: 5 November 1996     

Doubly resonant continuous-wave optical parametric oscillator pumped by a single-mode diode laser

The performance characteristics of a doubly (signal and idler) resonant continuous-wave optical parametric oscillator based on periodically poled lithium niobate and pumped by a 100-mW single-mode laser diode at 810 nm are reported. Pump power thresholds as low as 16 mW and wavelength tuning over the range 1.15-1.25 microm at the signal and 2.31-2.66 microm at the idler were achieved through variation of crystal temperature, pump wavelength, and grating period. Up to 5 mW of signal output was obtained with the single-mode diode pump, and signal powers of up to 39 mW were obtained when pumping with a 400-mW injection-locked broad-area diode laser.     

Acetylene detection based on diode laser QEPAS: combined wavelength and residual amplitude modulation

Quartz-enhanced photoacoustic spectroscopy (QEPAS) is demonstrated for acetylene detection at atmospheric pressure and room temperature with a fiber-coupled distributed feedback (DFB) diode laser operating at ~1.53 μm. An efficient approach for gas concentration calibration is demonstrated. The effect of residual amplitude modulation on the performance of wavelength modulated QEPAS is investigated theoretically and experimentally. With optimized spectrophone parameters and modulation depth, a minimum detectable limit (1σ) of ~2 part-per-million volume (ppmv) was achieved with an 8.44-mW diode laser, which corresponds to a normalized noise equivalent coefficient (1σ) of 6.16 × 10^?8 cm^?1 W/Hz^1/2.     

Dual‐wavelength monolithic Y‐branch distributed Bragg reflection diode laser at 671 nm suitable for shifted excitation Raman difference spectroscopy

A dual‐wavelength monolithic Y‐branch distributed Bragg reflection (DBR) diode laser at 671 nm is presented. The device is realized with deeply etched surface DBR gratings by one‐step epitaxy. A maximum optical output power of 110 mW is obtained in cw‐operation for each laser cavity. The emission wavelengths of the device are 670.5 nm and 671.0 nm with a spectral width of 13 pm (0.3 cm⁻¹) and a mean spectral distance of 0.46 nm (10.2 cm⁻¹) over the whole operating range. Together with a free running power stability of ± 1.1% this most compact diode laser is ideally suited as an excitation light source for portable shifted excitation Raman difference spectroscopy (SERDS).     

High resolution ethylene absorption spectrum between 6035 and 6210 cm-1

A two-channel photo-acoustic spectrometer (PA spectrometer) with a near infrared diode laser was used for taking measurements of a high resolution ethylene absorption spectrum. A semiconductor TEC-100 laser with an outer resonator generates a continuous single-frequency radiation in the range 6030–6300 cm^-1. A newly designed model of photo-acoustic detector (PAD) in the form of a ring type resonator provides for measurement of weak absorption cross-section equal to 4×10^-23 cm²/mol at a laser radiation power of 3 mW. The PAD threshold sensitivity is 2×10^-9 cm^-1 Hz^-1/2 W, when the signal to noise ratio equals to 1. The ethylene absorption spectrum within the range 6035–6210 cm^-1 was measured for the first time with a spectral resolution of 10 MHz. The reported line centre positions have an uncertainty of ± 0.0005 cm^-1. The precise measurements of ethylene absorption cross-sections were carried out using the mixture of high purity ethylene and broadening gas (nitrogen) at the mixture ratio 1:50–1:200. Measurements were carried out at a mixture pressure of about 4.2 kPa. PACS 42.62.Fi; 42.55.Px     

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.     

Mid-infrared generation and spectroscopy with a PPLN ridge waveguide

We have utilised a periodically poled LiNbO₃ crystal with a waveguide structure to produce up to 146 μW of mid-IR radiation around 2976 cm^-1 by difference frequency mixing of 1064 nm pump radiation with 1558 nm signal radiation. A conversion efficiency of 45% W^-1 is achieved within a crystal of length 50 mm, and temperature tuning curves are reported. The resultant idler radiation is exploited for high resolution absorption studies of both methane and methanethiol. The absorption cross-sections for methanethiol in the region of 2979 cm^-1 are measured and found to be ∼10^-19 cm², the relevance of these results to breath and headspace analysis of clinical samples containing volatile sulphur compounds is briefly discussed. PACS 42.62.Fi; 42.65.Ky     

Simultaneous detection of methane, oxygen and water vapour utilising near-infrared diode lasers in conjunction with difference-frequency generation

An all-diode-laser-based spectrometer is used for the simultaneous detection of methane, oxygen and water vapour. This is accomplished using a 760-nm diode laser and a 980-nm diode laser in conjunction with difference-frequency generation to 3.4 μm in a periodically poled lithium niobate crystal. Each of the output wavelengths is resonant with one of the molecular species. Simultaneous recordings over a 15-m open path of laboratory air are demonstrated. The recording scheme shows the wide applicability of a diode-laser-based difference-frequency spectrometer for the detection of molecular species in different wavelength ranges. By increasing the frequency of the 760-nm diode laser and decreasing the frequency of the 980-nm diode laser, a maximum continuous tuning range in the mid infrared of 3.6 cm^-1 is achieved. This enables the recording of several methane lines at atmospheric pressure. Pressure-dependence studies of methane lineshapes are also performed in an absorption cell. An indoor-air methane background level of 3 ppm is measured. The signal-to-noise ratio in the recorded methane spectra indicates that sub-ppm detection of methane at atmospheric pressure is feasible. Received: 6 March 2000 / Revised version: 19 June 2000 / Published online: 11 October 2000     

Development of a tunable mid-IR difference frequency laser source for highly sensitive airborne trace gas detection

The development of a compact tunable mid-IR laser system at 3.5 μm for quantitative airborne spectroscopic trace gas absorption measurements is reported. The mid-IR laser system is based on difference frequency generation (DFG) in periodically poled LiNbO₃ and utilizes optical fiber amplified near-IR diode and fiber lasers as pump sources operating at 1083 nm and 1562 nm, respectively. This paper describes the optical sensor architecture, performance characteristics of individual pump lasers and DFG, as well as its application to wavelength modulation spectroscopy employing an astigmatic Herriott multi-pass gas absorption cell. This compact system permits detection of formaldehyde with a minimal detectable concentration (1σ replicate precision) of 74 parts-per-trillion by volume (pptv) for 1 min of averaging time and was achieved using calibrated gas standards, zero air background and rapid dual-beam subtraction. This corresponds to a pathlength-normalized replicate fractional absorption sensitivity of 2.5×10^-10 cm^-1. Received: 29 April 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-303/497-1492, E-mail: dr@ucar.edu     

Low-threshold singly-resonant continuous-wave optical parametric oscillator based on MgO-doped PPLN

We present a 532 nm-pumped singly-resonant cw optical parametric oscillator based on MgO-doped PPLN with a minimum threshold pump power of 0.3 W. The OPO with a two-mirror standing-wave cavity is optimized by using a tunable diode laser on the path of the resonant signal beam. The maximum output power is 200 mW at an idler wavelength near 1330 nm at a pump power of 2 W. We report the degradation of the output power and beam characteristics at high pump power indicating a strong thermal lensing in the crystal. The continuous tuning range of the OPO is measured to be 800 MHz which is close to 90% of the free spectral range of the OPO cavity.     

Mid-infrared fiber-coupled QCL-QEPAS sensor

An innovative spectroscopic system based on an external cavity quantum cascade laser (EC-QCL) coupled with a mid-infrared (mid-IR) fiber and quartz enhanced photoacoustic spectroscopy (QEPAS) is described. SF₆ has been selected as a target gas in demonstration of the system for trace gas sensing. Single mode laser delivery through the prongs of the quartz tuning fork has been obtained employing a hollow waveguide fiber with inner silver–silver iodine (Ag–AgI) coatings and internal core diameter of 300 μm. A detailed design and realization of the QCL fiber coupling and output collimator system allowed almost practically all (99.4 %) of the laser beam to be transmitted through the spectrophone module. The achieved sensitivity of the system is 50 parts per trillion in 1 s, corresponding to a record for QEPAS normalized noise-equivalent absorption of 2.7 × 10^?10 W cm^?1 Hz^?1/2.     

Limitations of an optically pumped rubidium laser imposed by atom recycle rate

A rubidium laser pumped on the 5²S_1/2–5²P_3/2 D₂ transition by a pulsed dye laser at pump intensities exceeding 3.5 MW/cm² (>1000 times threshold) has been demonstrated. Output energies as high as 12 μJ/pulse are limited by the rate for collision relaxation of the pumped ²P_3/2 state to the upper laser ²P_1/2 state. More than 250 photons are available for every rubidium atom in the pumped volume during each pulse. For modest alkali atom and ethane spin–orbit relaxer concentrations, the gain medium can only process about 50 photons/atom during the 2–8 ns pump pulse. At 110°C and 550 Torr of ethane, the system is bottlenecked in the ²P_3/2 state and all of the incident photons cannot be absorbed. The output energy is linearly dependent on pump pulse duration for a given pump energy. The highly saturated pump limit of the recently developed three-level model for diode pumped alkali lasers (DPALs) is developed. The system efficiency based on absorbed photons approaches 36% even for these extreme pump conditions.     

Comparison of cw laser performance of Nd:KGW, Nd:YAG, Nd:BEL, and Nd:YVO4 under laser diode pumping

4 crystals under low-power laser diode end-pumping. Output power dependencies on the pump power and the pump wavelength of these diode-pumped solid state lasers were investigated. The high Nd³⁺ concentration of the Nd:KGW samples used in our measurements as well as up-conversion and exited-state absorption processes in Nd:KGW cause the reduced laser output power dependence on the pump wavelength which was experimentally observed. At pump levels up to 270 mW a slope efficiency of η_sl≈46% was reached for the Nd:KGW laser. Nd:KGW microchip laser operation with a slope efficiency of η_sl≈50% was demonstrated. Thermal lensing in Nd:KGW at pump powers up to 3 W was measured. Received: 4 August 1997