J. Manne

Pulsed quantum cascade laser-based cavity ring-down spectroscopy for ammonia detection in breath

Breath analysis can be a valuable, noninvasive tool for the clinical diagnosis of a number of pathological conditions. The detection of ammonia in exhaled breath is of particular interest for it has been linked to kidney malfunction and peptic ulcers. Pulsed cavity ringdown spectroscopy in the mid-IR region has developed into a sensitive analytical technique for trace gas analysis. A gas analyzer based on a pulsed mid-IR quantum cascade laser operating near 970 cm(-1) has been developed for the detection of ammonia levels in breath. We report a sensitivity of approximately 50 parts per billion with a 20 s time resolution for ammonia detection in breath with this system. The challenges and possible solutions for the quantification of ammonia in human breath by the described technique are discussed.

Off-axis cavity enhanced spectroscopy based on a pulsed quantum cascade laser for sensitive detection of ammonia and ethylene

A pulsed, distributed feedback (DFB) quantum cascade (QC) laser centered at 970 cm(-1) was used in combination with an off-axis cavity enhanced absorption (CEA) spectroscopic technique for the detection of ammonia and ethylene. Here, the laser is coupled into a high-finesse cavity with an optical path length of ∼76 m. The cavity is installed into a 53 cm long sample cell with a volume of 0.12 L. The laser is excited with short current pulses (5-10 ns), and the pulse amplitude is modulated with an external current ramp, resulting in a ∼0.3 cm(-1) frequency scan. A demodulation approach followed by numerical filtering was utilized to improve the signal-to-noise ratio. We demonstrated detection limits of ~15 ppb and ∼20 ppb for ammonia and ethylene, respectively, with less than 5 s averaging time.

Cavity ring-down spectroscopy with a pulsed distributed feedback quantum cascade laser

A pulsed distributed feedback quantum cascade laser operating near 970 cm-1 (10.3 μm) was coupled with the technique of cavity ring-down spectroscopy, as described here for the first time. The newly constructed set-up was tested by recording three relatively weak rotational lines of the 1000→0001 vibrational band of CO2 in the range from 966.75 cm-1 to 971.5 cm-1. The CO2 lines were recorded by measuring the decay time of a CO2 - N2 mixture flowing through an open sample tube placed between the cavity ring-down mirrors. The quantum cascade laser frequency was tuned at a rate of ~ 0.071 cm-1/K by changing the heat sink temperature in the range between -20 and 50 °C. The first results demonstrated the applicability and high sensitivity of the cavity ring-down spectroscopy - pulsed quantum cascade laser combination and encouraged us to extend our research to the study and detection of ammonia. We demonstrated that a detection limit of ammonia of ~ 25 ppbv can be attained with the current set-up. Basic instrument performance and optimization of the experimental parameters for sensitivity improvement are discussed.

A quantum cascade laser based room temperature spectrometer for sensitive detection of ammonia and ethylene

We investigated the use of a pulsed, distributed feedback (DFB) quantum cascade (QC) laser centered at 970 cm-1 in combination with an astigmatic Herriot cell with 150 m path length for the detection of ammonia and ethylene. This spectrometer utilizes the intra-pulse method, where a linear frequency down-chirp, that is induced when a top-hat current pulse is applied to the laser, is used for sweeping across the absorption line. This provides a real time display of the spectral fingerprint of molecular gases, which can be a few wave numbers wide. A 200 ns long pulse was used for these measurements which resulted in a spectral window of ~1.74 cm-1. A room temperature mercury-cadmium-telluride detector was used, resulting in a completely cryogen free spectrometer. We demonstrated detection limits of ~3 ppb for ammonia and ~5 ppb for ethylene with less than 10 s averaging time.

Wavelength modulation spectroscopy with a pulsed quantum cascade laser for the sensitive detection of acrylonitrile

A pulsed, distributed feedback (DFB) quantum cascade laser centered at 957 cm−1 was used in combination with a wavelength modulation spectroscopic technique for the detection of acrylonitrile. The laser was excited with short current pulses (5–10 ns), and the pulse amplitude was modulated with a linear subthreshold current ramp at 20 Hz resulting in a ∼2.5 cm−1 frequency scan. This allowed the measurement of spectroscopic features of acrylonitrile with absorption line widths of ∼1 cm−1. A demodulation approach followed by numerical filtering was utilized to improve the signal-to-noise ratio. We then superimposed a 10 kHz sine wave current modulation on top of the 20 Hz current ramp. The resulting high frequency temperature modulation of the DFB structure results in wavelength modulation. A minimum detectable absorbance of ∼10−5, corresponding to the sub 109 levels of acrylonitrile, was achieved with less than a minute averaging time.

Detection of acrolein and acrylonitrile with a pulsed room temperature quantum cascade laser

We investigated the use of a pulsed, distributed feedback quantum cascade laser centered at 957 cm-1 in combination with an astigmatic Herriot cell with 250 m path length for the detection of acrolein and acrylonitrile. These molecules have been identified as hazardous air-pollutants because of their adverse health effects. The spectrometer utilizes the intra-pulse method, where a linear frequency down-chirp, that is induced when a top-hat current pulse is applied to the laser, is used for sweeping across the absorption line. Up to 450 ns long pulses were used for these measurements which resulted in a spectral window of ~2.2 cm-1. A room temperature mercury-cadmium-telluride detector was used, resulting in a completely cryogen free spectrometer. We demonstrated detection limits of ~3 ppb for acrylonitrile and ~6 ppb for acrolein with ~10 s averaging time. Laser characterization and optimization of the operational parameters for sensitivity improvement are discussed.

Pulsed quantum cascade laser based cavity ring-down and cavity enhanced spectroscopy for the detection of ethylene.

We investigated the use of a pulsed, distributed feedback (DFB) quantum cascade (QC) laser centered at 970 cm-1 in combination with cavity ring-down spectroscopy (CRDS) and cavity enhanced spectroscopic (CES) techniques for the detection of ethylene. In these techniques, the laser is coupled to a high-finesse cavity formed by high reflectivity mirrors. In the CRDS application, the laser frequency was tuned at a rate of ~0.071 cm-1/K by changing the heat sink temperature in the range between -20 and 50°C. For off-axis CES, the laser was excited with short current pulses (5-10 ns), and the pulse amplitude was modulated with an external current ramp which gave a frequency scan of ~0.3 cm-1. We utilized a demodulation approach followed by numerical filtering to improve the signal-to-noise ratio. Basic instrument performance and optimizations of the experimental parameters for sensitivity improvement are discussed. We demonstrated a detection limit of ~130 ppb with CRDS and ~15 ppb with off-axis CES for ethylene.

Wavelength modulation spectroscopy with a pulsed quantum cascade laser

A pulsed distributed feedback quantum cascade laser (QCL) operating near 957 cm-1 was employed in wavelength modulation mode for spectroscopic trace gas sensing applications. The laser was excited with short current pulses (5-10 ns) with < 2% duty cycle. The pulse amplitude was modulated with a linear sub-threshold current ramp at 20 Hz resulting in a ~ 2.5 cm-1 frequency scan, which is typically wider than what has been reported for these lasers, and would allow one to detect molecular absorption features with line widths up to 1 cm-1. A demodulation approach followed by numerical filtering was utilized to improve the signal-to-noise ratio. We then superimposed a sine wave current modulation at 10 kHz onto the 20 Hz current ramp. The resulting high frequency temperature modulation of the distributed feedback (DFB) structure results in wavelength modulation (WM). The set-up was tested by recording relatively weak absorption lines of carbon dioxide. We demonstrated a minimum detectable absorbance of 10-5 for this spectrometer. Basic instrument performance and optimization of the experimental parameters for sensitivity improvement are discussed.